Liquid crystalline compound having dienyl moiety and liquid crystal composition

ABSTRACT

The present invention is to provide a liquid crystalline 
     The present invention is concerned with a liquid crystalline compound expressed by general formula (1) ##STR1## wherein R 1  represents cyano group, halogen atom, or a straight or branched alkyl group or halogenated alkyl group having 1 to 20 carbon atoms, one or not-adjacent two CH 2  groups in the alkyl group or halogenated alkyl group may be replaced by oxygen atom or --CH═CH-- group; R 2  and R 2  &#39; represent hydrogen atom, halogen atom, or an alkyl group having 1 to 9 carbon atoms; X 1 , X 2 , and X 3  independently represent --CH 2  CH 2  --, --CO--O--, --O--CO--, --CH═CH--, --C.tbd.C--, --(CH 2 ) 4  --, --CF 2  O--, --OCF 2  --, --CH 2  O--, --OCH 2  --, or a covalent bond; rings A, B, C, and D independently represent 1,4-phenylene ring, trans-1,4-cyclohexylene ring, bicyclo[1,1,0]butane ring, bicyclo[1,1,1]pentane ring, bicyclo[3,2,2]octane ring, cyclobutane ring, or spiro[3,3]heptane ring, respectively, hydrogen atom in these rings may be replaced by halogen atom and carbon atom in these rings may be replaced by nitrogen atom or oxygen atom; l, m, and o are independently 0 or 1, n is an integer of 0 to 3, and p is an integer of 1 to 5.

This application is a divisional application of Ser. No. 08/890,547 filed Jul. 9, 1997, now U.S. Pat. No. 6,001,275 which is a 371 of PCT/JP96/00083 filed Jan. 19, 1996.

TECHNICAL FIELD

The present invention relates to a novel liquid crystalline compound which develops preferable physical properties and to a liquid crystal composition comprising the novel liquid crystalline compound mentioned above and having preferable physical properties.

BACKGROUND ART

Liquid crystal display devices employ the optical anisotropy and dielectric anisotropy of liquid crystal compounds. As their display mode, twisted nematic mode (TN mode), super twisted nematic mode (STN mode), dynamic scattering mode (DS mode), guest-host mode (GH mode), and DAP mode are known. As their driving mode, static driving mode, time sharing addressing mode, active matrix driving mode, and dual frequency driving mode are known.

Whereas the properties of liquid crystalline compounds used for these liquid crystal display devices are different depending on their uses, it is required of any of the liquid crystalline compounds that they are stable against external environmental factors such as moisture, air, heat, and light, and that they exhibit a liquid crystal phase at a range of temperatures as wide as possible with room temperature preferably being at its center.

Liquid crystal compositions are composed of several or twenty-odd liquid crystalline compounds to develop most suitable characteristics required of a particular display device. Therefore, liquid crystalline compounds are required to be excellent in miscibility with other liquid crystalline compounds, even in the miscibility at low temperatures particularly from the latest demand for their use in various environment.

Especially, steep threshold characteristics are required of liquid crystal compositions used in STN driving to actualize high picture quality. The steepness is a function of the ratio of elastic constants K₃₃ /K₁₁, and it is known that the larger the ratio of the elastic constants of liquid crystalline compounds are used in a liquid crystal composition, the steeper threshold characteristics the composition exhibits (F. Leenhouts et al., Proceedings of the Japan Display, 388 (1986)).

Also, it is necessary to use a liquid crystal composition having a high response speed for realizing a large screen of display device. It is known that the response speed is a function of viscosity (E. Jakeman et al., Phys. Lett., 39A, 69 (1972)). That is, it is important to use liquid crystalline compounds having a low viscosity necessary for actualizing a composition having a low viscosity.

As the compound having a large elastic constant ratio K₃₃ /K₁₁, compounds which have an alkenyl moiety are known. That is, they are the compounds described in M. Schadt et al., Mol. Cryst. Liq. Cryst., 122 (1985) and Laid-open Japanese Patent Publication No. Sho 61-83136; and the compounds having introduced fluorine atom and described in Japanese Patent Application No. Hei 6-92740, each of which are shown below. ##STR2##

Any of these alkenyl compounds has a large ratio of elastic constants K₃₃ /K₁₁ (about 1.78 to 2.28) and liquid crystal compositions comprising these compounds exhibit a preferable steepness. (Elastic constant ratio K₃₃ /K₁₁ of the four compounds mentioned above are the values determined under the same conditions as in Example 7 (Use Example 1) mentioned below.) However, as the demand on the displaying ability of liquid crystal display devices has increased, liquid crystal compositions having a higher response speed, in other words, liquid crystal compositions having a lower viscosity have been demanded.

As the compounds having a large elastic constant ratio K₃₃ /K₁₁, compounds having 1,3-butadienyl group are described in Laid Open Japanese Patent Publication No. Hei 6-151445. ##STR3##

However, since the substituent, 1,3-butadienyl group has a conjugated diene moiety, the compound is chemically very unstable, and thus it was impossible to use the compound in liquid crystal compositions to be practically used.

In short, liquid crystalline compounds are long-awaited which have a large elastic constant ratio K₃₃ /K₁₁, still lower viscosity compared with that of known liquid crystalline compounds, high chemical stability, and excellent miscibility with other liquid crystalline compounds.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a novel liquid crystalline compound which has a large ratio of elastic constants, has a low viscosity compared with that of known liquid crystalline compounds, is excellent in miscibility with other liquid crystalline compounds, particularly in the miscibility at low temperatures, and is chemically stable, and to provide a liquid crystal composition containing the compound. As a result of the diligent investigation by the present inventors to solve the problems mentioned above, compounds have been found which have a novel structure and have improved characteristics compared with those of known liquid crystalline compounds, leading to the achievement of the present invention.

First aspect of the present invention is concerned with a liquid crystalline compound having an unconjugated alkadienyl group at a side chain.

Second aspect of the present invention is concerned with a liquid crystalline compound expressed by general formula (1) ##STR4## wherein R₁ represents cyano group, halogen atom, or a straight or branched alkyl group or halogenated alkyl group having 1 to 20 carbon atoms, one or not-adjacent two CH₂ groups in the alkyl group or halogenated alkyl group may be replaced by oxygen atom or --CH═CH-- group; R₂ and R₂ ' represent hydrogen atom, halogen atom, or an alkyl group having 1 to 9 carbon atoms; X₁, X₂, and X₃ independently represent --CH₂ CH₂ --, --CO--O--, --O--CO--, --CH═CH--, --C.tbd.C--, --(CH₂)₄ --, --CF₂ O--, --OCF₂ --, --CH₂ O--, --OCH₂ --, or a covalent bond; rings A, B, C, and D are independently represent 1,4-phenylene ring, trans-1,4-cyclohexylene ring, bicyclo[1,1,0] butane ring, bicyclo[1,1,1]pentane ring, bicyclo[3,2,2]octane ring, cyclobutane ring, or spiro[3,3]heptane ring, respectively, hydrogen atom in these rings may be replaced by halogen atom, carbon atom in these rings may be replaced by nitrogen atom or oxygen atom; l, m, and o are independently 0 or 1, n is an integer of 0 to 3, p is an integer of 1 to 5.

Third aspect of the present invention is concerned with a second compound of the present invention expressed by general formula (1) wherein n is 0, o is 1, p is 2, and R₂ and, R'₂ are hydrogen atom, respectively.

Fourth aspect of the present invention is concerned with a third compound of the present invention expressed by general formula (1) wherein at least one of X₁, X₂, and X₃ is a covalent bond.

Fifth aspect of the present invention is concerned with a fourth compound of the present invention expressed by general formula (1) wherein X₁, X₂, and X₃ are --CH₂ CH₂ --, --CH═CH--, --(CH₂)₄ --, or a covalent bond.

Sixth aspect of the present invention is concerned with a liquid crystal composition comprising at least two components and containing a compound recited in any one of the aspects 1 to 5 in at least one of the components.

Seventh aspect of the present invention is concerned with a liquid crystal composition containing, as a first component, at least one compound recited in any one of the aspects 1 to 5, and containing, as a second component, one or more compounds selected from the group consisting of the compounds expressed by general formula (2), (3), or (4) ##STR5## in which R₃ represents an alkyl group having 1 to 10 carbon atoms, Y represents F or Cl, Q₁ and Q₂ independently represent H or F, r is 1 or 2, and Z₁ and Z₂ independently represent --CH₂ CH₂ -- or a covalent bond.

Eighth aspect of the present invention is concerned with a liquid crystal composition containing, as a first component, at least one compound recited in any one of the aspects 1 to 5, and containing, as a second component, one or more compounds selected from the group consisting of the compounds expressed by general formula (5), (6), (7), (8), or (9) ##STR6## in which R₄ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in either case any methylene group (--CH₂ --) in the alkyl or alkenyl group may be replaced by oxygen atom (--O--) provided that in no case two or more methylene groups are continuously replaced by oxygen atom; Z₃ represents --CH₂ CH₂ --, --COO--, or a covalent bond, Q₃ and Q₄ represent H or F, E represents cyclohexane ring, benzene ring, or 1,3-dioxane ring, and s is an integer of 0 or 1, ##STR7## in which R₅ represents an alkyl group having 1 to 10 carbon atoms, Q₅ represents H or F, and k is an integer of 0 or 1, ##STR8## in which R₆ represents an alkyl group having 1 to 10 carbon atoms, G represents cyclohexane ring or benzene ring, Q₆ and Q₇ independently represent H or F, respectively, Z₄ represents --COO-- or a covalent bond, and h is an integer of 0 or 1,

    R.sub.7 --(H)--Z.sub.5 --(J)--R.sub.8                      (8)

in which R₇ and R₈ independently represent an alkyl group, alkyloxyl group, or alkyloxymethyl group having 1 to 10 carbon atoms, H represents cyclohexane ring, pyrimidine ring, or benzene ring, J represents cyclohexane ring or benzene ring, Z₅ represents --C.tbd.C--, --COO--, --CH₂ CH₂ --, or a covalent bond, ##STR9## in which R₉ represents an alkyl group or alkoxyl group having 1 to 10 carbon atoms, R₁₀ represents an alkyl group, alkyloxyl group, or alkoxymethyl group having 1 to 10 carbon atoms, K represents cyclohexane ring or pyrimidine ring, each of L and M independently represent cyclohexane ring or benzene ring, Z₆ represents --COO--, --CH₂ CH₂ --, or a covalent bond, Z₇ represents --C.tbd.C--, --COO--, or a covalent bond, and Q₈ represents H or F.

Ninth aspect of the present invention is concerned with a liquid crystal display device comprising a liquid crystal composition recited in any one of the aspects 6 to 8.

Tenth aspect of the present invention is concerned with a liquid crystal display device comprising a liquid crystal composition recited in any one of the aspects 6 to 9.

Preferable compounds of the present invention recited in the aspects 1 to 5 are those expressed by the group of the following general formulas (1-a) to (1-c). However, W in the following formulas represents

--(CH₂)_(n) --(CH)_(o) ═CH--(CH₂)_(p) --CH═CH--R₂ R₂ ' in general formula (1), and R₁, R₂, R₂ ', X₁, X₂, X₃, rings A, B. C, and D, and l, m, n, o, and p have the same meaning as mentioned above. ##STR10##

Further, among the compounds expressed by the group of general formulas (1-a) to (1-c), particularly preferable compounds are shown below: ##STR11## whereas R₁ and W in the formulas shown above have the same meaning as that mentioned above, hydrogen atom in 1,4-phenylene ring, trans-1,4-cyclohexylene ring, bicyclo[1,1,0]butane ring, bicyclo[1,1,1] pentane ring, bicyclo[3,2,2]octane ring, cyclobutane ring, and spiro[3,3]heptane ring may be replaced by halogen atom, and the carbon atom in the rings may be replaced by nitrogen atom or oxygen atom.

While any of dienyl group W exhibits preferable characteristics when it satisfies the conditions shown by general formula (1), particularly preferable ones are W₁ to W₁₅, W₁₇, and W₁₉, and more desirable ones are W₁ to W₈, and W₁₇ shown below: ##STR12## While R₁ in the formulas shown above represents cyano group, halogen atom, or a straight or branched alkyl group or halogenated alkyl group in the alkyl or halogenated alkyl group having 1 to 20 carbon atoms, methylene group may be replaced by oxygen atom or --CH═CH--. As the halogen atom, fluorine atom and chlorine atom, and as the alkyl group, one having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms is preferable. Further, as the halogenated alkyl group, trifluoromethyl, trifluoromethoxy, difluoromethoxy, 2-fluoro-ethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 2-fluoro-propyl, 2,2-difluoropropyl, 4-fluorobutyl, 3-fluoro-butyl, 2-fluorobutyl, 3,3-difluorobutyl, 2,2-difluorobutyl, 5-fluoropentyl, 4-fluoropentyl, 3-fluoropentyl, 3,3-difluoro-pentyl, and 10-fluorodecyl are preferable. As the one in which methylene group is replaced by oxygen atom, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentoxymethyl, methoxyethoxy, methoxypropyl, ethoxyethoxy, and ethoxypropoxyl group are preferable. As the one in which methylene group is replaced by --CH═CH--, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, and 3-pentenyl group are preferable.

Any of the compounds of the present invention expressed by general formula (1) has a large elastic constant ratio K₃₃ /K₁₁ and a low viscosity. Further, any of them is an unconjugated diene and chemically very stable.

Any of the compounds of the present invention exhibits preferable physical properties, and liquid crystal compositions which have characteristics satisfying the purpose can be produced by using compounds expressed by general formula (1) and in which R₁, R₂, R₂ ', X₁, X₂, X₃, A, B, C, D, l, m, n, o, and p are suitably selected. For instance, when a compound is used for a liquid crystal composition mesomorphic range of which must be particularly in a high temperature side, a tricyclic or tetracyclic compound can be used, and in other cases, bicyclic or tricyclic compound can be used.

When especially a large dielectric anisotropy is required, a compound having a positive dielectric anisotropy (P type compound) is used as in the case for compositions commonly used, and a P type compound can be provided by selecting halogen atom or cyano group as R₁ in general formula (1). Besides, when a still larger dielectric anisotropy is required, the purpose is achieved by introducing halogen atom on a ring to which R₁ is linked. In order to obtain a compound having a negative dielectric anisotropy (N type compound), it will be sufficient to introduce a substituent having a not-large dipole moment, for example, an alkyl group as R₁.

Optical anisotropy can also be controlled by optionally selecting R₁, R₂, R₂ ', X₁, X₂, X₃, A, B, C, D, l, m, n, o, and p in general formula (1). That is, when a large optical anisotropy is required, it is sufficient to use a compound having more 1,4-phenylene rings; and a compound having a more trans-1,4-cyclohexylene rings when a small optical anisotropy is required.

Compounds of the present invention expressed by general formula (1) can readily be produced by freely using the ordinary technique in organic synthetic chemistry as indicated by the reaction formulas shown below: ##STR13## in the formula shown above, ring D represents a substituted or unsubstituted 1,4-phenylene ring or trans-1,4-cyclohexylene a ring, hydrogen atom in the ring may be replaced by halogen atom, and the carbon atom in the ring may be replaced by nitrogen atom or oxygen atom, and X represents halogen atom.

That is, when o and n are 0, the compound expressed by general formula (1) can be produced by reacting a phosphonium salt such as (11) with a cyclohexanone (10) in the presence of a base. The phosphonium salt can readily be produced from a corresponding halide and triphenylphosphine according to the method of G. Wittig et al. described in Org. Synth. Col. V. 751 (1973). As the base, for example, alkyl lithium, sodium hydride, and potassium-t-butoxide can preferably be used.

When o is 1, (1) can be obtained by reacting (11) with an aldehyde expressed by (12) according to the method of G. Wittig et al. described in Org. Synth. Col. V. 751 (1973). Whereas the reaction of (11) with (12) usually gives a cis form olefin as main product, it can be derived to (1) which is in trans form by converting the olefin into a bromide (13), removing unnecessary isomers by recrystallization, and then reducing the bromide according to the method of J. Schaeffer et al. described in Org. Synth. Col. V. 249 (1973). While the method in which the olefin is once oxidized to form an epoxide and then reacted with triphenylphosphine dibromide is preferable for the bromination, there is no problem in directly reacting bromine of simple substance with an olefin. While the reduction of (13) can readily be performed by either method, the use of metal zinc according to the method of S. J. Cristol et al. described in J. Am. Chem. Soc., 89, 401 (1967) is preferable.

Cyclohexanone (10) can readily be produced from, for example, a halide (14). That is, (10) can be preferably produced by converting (14) into Grignard reagent or lithium reagent, reacting it with an available cyclohexanone derivative (15), and then subjecting to a dehydration, reduction, and deprotection.

Also, aldehyde (12) can be produced from a carboxylic acid (16), which can be obtained by a method described in literatures, for example, the method of M. E. Neubert et al. described in Mol. Cryst. Liq. Cryst., 76, 48 (1981), by utilizing a two carbons homologation reaction ordinarily used.

When X₁, X₂, and X₃ in general formula (1) are --CH₂ CH₂ --, main skeleton can be constructed according to the method of Laid-open Japanese Patent Publication No. Hei 5-140015 and when they are --(CH₂)₄ --, can be constructed according to the method of Laid-open Japanese Patent Publication No. Hei 5-310605. When they are --CH═CH-- or --C.tbd.C--, it can be produced by the method of Laid-open Japanese Patent Publication No. Hei 6-92924 and C. E. Castro et al. described in Org. Chem., 28, 2163, 3313 (1963), respectively. When they are --CF₂ O-- or --OCF₂ --, it can be produced according to the method of Laid-open Japanese Patent Publication No. Hei 5-112778, and when they are --CH₂ O-- or --OCH₂ --, it can be produced according to the method of Japanese Patent Publication No. Hei 2-6743. Also, when they are --COO-- or --OCO--, it can preferably be produced according to the method of B. K. Sadashiva, Mol. Cryst. Liq. Cryst., 55, 135 (1979).

Liquid crystal composition of the present invention preferably contains at least one compound expressed by general formula (1) in a ratio of 0.1 to 99% by weight to develop excellent characteristics.

Specifically, liquid crystal compositions of the present invention can be produced by blending a compound optionally selected, depending on the purpose, from the group of compounds expressed by any one of general formulas (2) to (9) to the first component containing at least one compound expressed by general formula (1).

As the compounds used in liquid crystal compositions of the present invention and expressed by any one of general formulas (2) to (4), the following compounds can preferably be mentioned:

(In the followings, Ra represents an alkyl group or alkoxy group.) ##STR14##

Compounds expressed by any one of general formulas (2) to (4) are ones which have a positive dielectric anisotropy, are remarkably excellent in heat resistance and chemical resistance, and are indispensable compounds when liquid crystal compositions for TFT (AM-LCD) are produced of which TFT high reliability demonstrated, for instance, by an especially high voltage holding ratio and a large specific resistance is required.

While the compounds expressed by any one of general formulas (2) to (4) can optionally be used in the range of 1 to 99% by weight based on the total amount of liquid crystal composition when liquid crystal compositions for TFT are produced, the use in an amount of 10 to 97% by weight is preferable and 40 to 95% by weight is more desirable. Also at that time, a compound expressed by any one of general formulas (5) to (9) may be contained as a part of the composition. Even when liquid crystal compositions for STN display mode or ordinary TN display mode are produced, a compound expressed by any one of general formulas (2) to (4) can be used.

As the compounds expressed by any one of general formulas (5) to (7), the following compounds can preferably mentioned:

(In the followings, Rb, Rc, and Rd represent an alkyl group or alkenyl group, and R' represents an alkylene.) ##STR15##

Compounds expressed by any one of general formulas (5) to (7) have a large positive dielectric anisotropy and are used particularly for the purpose of lowering threshold voltage. They are also used for the purpose of adjusting viscosity and optical anisotropy, and of widening nematic range by, for instance, raising clearing point. Further, they are used for the purpose of improving the steepness.

As the compounds of the present invention expressed by general formula (8) or (9), the following compounds can preferably be mentioned:

(In the followings, Re, Rf, Rg, and Rh represent an alkyl group or alkenyl group.) ##STR16##

Compounds expressed by general formula (8) or (9) are ones having a negative or small positive dielectric anisotropy. Compounds expressed by general formula (8) are used for the purpose of principally reducing viscosity and/or adjusting optical anisotropy. Compounds expressed by general formula (9) are used for the purpose of widening nematic range by, for instance, raising clearing point and/or adjusting optical anisotropy.

Compounds expressed by any one of general formulas (5) to (9) are indispensable particularly when liquid crystal compositions for STN display mode or ordinary TN display mode are produced.

While the compounds of general formulas (5) to (9) can optionally be used in the range of 1 to 99% by weight when liquid crystal compositions for ordinary TN display mode or STN display mode are produced, the use in an amount of 10 to 97% by weight is preferable, and 40 to 95% by weight is more desirable. Also at that time, a compound expressed by any one of general formulas (2) to (4) may be used as a part of the composition.

By using the liquid crystal compositions of the present invention for TFT liquid crystal display devices, steepness and viewing angle can be improved. Also, since the compounds expressed by general formula (1) have a low viscosity, the response speed of the liquid crystal display devices comprising the compounds can be improved.

Liquid crystal compositions used according to the present invention are produced by the methods which are conventional in the art. Generally, methods are adopted in which various components are dissolved with each other at a high temperature. Also, liquid crystal materials of the present invention are improved, depending on the intended uses, by using a suitable additive to optimize. Such additives are well known in the art and described in literatures in detail. Usually, a chiral dopant or likes are added to cause a helical structure of liquid crystal to adjust a required twisting angle, and to avoid reverse-twist.

Further, the liquid crystal compositions of the present invention can be used as liquid crystal compositions for guest-host (GH) mode by adding a dichroic dye such as merocyanine type, styryl type, azo type, azomethine type, azoxy type, quinophthalone type, anthraquinone type, and tetrazine type dye. Alternatively, they can also be used as liquid crystal compositions for polymer dispersion type liquid crystal display devices (PDLCD) typified by NCAP which is prepared by forming a nematic liquid crystal into a microcapsule or typified by a polymer net work liquid crystal display devices (PNLCD) which is prepared by forming a polymer of three-dimensional network structure in a liquid crystal. Also, the liquid crystal compositions of the present invention can be used as ones for electrically controlled birefringence (ECB) mode or dynamic scattering (DS) mode.

As the nematic liquid crystal compositions containing the compounds of the present invention and produced by the methods mentioned above, composition examples can be shown as follows:

    ______________________________________                                         Composition Example 1                                                          4-(1,5-hexadienyl)-4'-pentylbicyclohexane                                                                  17%                                                3,5-difiuoro-4-cyanophenyl-4-(3-pentenyl)benzoate                                                           8%                                                4-(4-propylcyclohexyl)benzonitrile                                                                         24%                                                4-(4-propylcyclohexyl)ethoxybenzene                                                                         6%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                          10%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)propylbenzene                                                          16%                                                4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)                                                        7%                                                ethylbenzene                                                                   4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethenyl)                                                        4%                                                ethylbenzene                                                                   4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethenyl)                                                        4%                                                propylbenzene                                                                  4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethenyl)                                                        4%                                                butylbenzene                                                                   Composition Example 2                                                          4-(1,5-hexadienyl)-4'-ethylbicyclohexane                                                                    8%                                                4-(1,5-hexadienyl)-4'-propylbicyclohexane                                                                   8%                                                4-(1,5-hexadienyl)-4'-pentylbicyclohexane                                                                   8%                                                4-(4-(3-butenyl)cyclohexyl)benzonitrile                                                                    10%                                                4-(4-(3-pentenyl)cyclohexyl)benzonitrile                                                                   10%                                                4-(4-propylcyclohexyl)benzonitrile                                                                         10%                                                3,5-difluoro-4-cyanophenyl-4-(3-pentenyl)benzoate                                                           3%                                                4-(4-propylcyclohexyl)ethoxybenzene                                                                         3%                                                4-(2-(4-butylphenyl)ethynyl)ethoxybenzene                                                                   6%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methoxybenzene                                                          5%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                          10%                                                4-(2-(4-(2-(4-ethylcyclohexyl)ethyl)phenyl)ethenyl)                                                         3%                                                ethylbenzene                                                                   4-(2-(4-(2-(4-ethylcyclohexyl)ethyl)phenyl)ethenyl)                                                         3%                                                butylbenzene                                                                   4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethenyl)                                                        3%                                                ethylbenzene                                                                   4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethenyl)                                                        3%                                                propylbenzene                                                                  4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethenyl)                                                        3%                                                butylbenzene                                                                   4-(4-(4-propylcyclohexyl)cyclohexyl)fluorobenzene                                                           4%                                                Composition Example 3                                                          4-(4-(1,5-hexadienyl)cyclohexyl)benzonitrile                                                               10%                                                4-(4-(1,5-hexadienyl)cyclohexyl)propylbenzene                                                              10%                                                4-(4-ehtylcyclohexyl)benzonitrile                                                                           3%                                                4-(4-propylcyclohexyl)benzonitrile                                                                         20%                                                4-cyanophenyl-4-ethylbenzoate                                                                               6%                                                4-cyanophenyl-4-propylbenzoate                                                                              3%                                                4-(2-(4-ethylphenyl)ethynyl)methoxybenzene                                                                  3%                                                4-(2-(4-propylphenyl)ethynyl)methoxybenzene                                                                 3%                                                4-(2-(4-butylphenyl)ethynyl)methoxybenzene                                                                  3%                                                4-(2-(4-pentylphenyl)ethynyl)methoxybenzene                                                                 3%                                                4-(2-(4-butylphenyl)ethynyl)ethoxybenzene                                                                   3%                                                4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)                                                        6%                                                ethylbenzene                                                                   4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)                                                        6%                                                propylbenzene                                                                  4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)                                                        6%                                                butylbenzene                                                                   4-(2-(4-(2-(4-ethylcyclohexyl)ethynyl)phenyl)ethynyl)                                                       3%                                                ethylbenzene                                                                   4-(2-(4-(2-(4-ethylcyclohexyl)ethynyl)phenyl)ethynyl)                                                       3%                                                propylbenzene                                                                  4-(2-(4-(2-(4-propylcyclohexyl)ethynyl)phenyl)ethynyl)                                                      3%                                                ethylbenzene                                                                   4-(2-(4-(2-(4-propylcyclohexyl)ethynyl)phenyl)ethynyl)                                                      3%                                                propylbenzene                                                                  4-(2-(4-(2-(4-propylcyclohexyl)ethynyl)phenyl)ethynyl)                                                      3%                                                butylbenzene                                                                   Composition Example 4                                                          4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                              7%                                                methylbenzene                                                                  4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                             10%                                                benzonitrile                                                                   2-(3,4-difluorophenyl)-5-propylpyrimidine                                                                   8%                                                2-fluoro-4-(4-ethylcyclohexyl)benzonitrile                                                                  8%                                                2-fluoro-4-(4-propylcyclohexyl)benzonitrile                                                                 8%                                                4-(4-propylcyclohexyl)benzonitrile                                                                          4%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)-1,2-difluorobenzene                                                     6%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)-1,2-difluorobenzene                                                    6%                                                4-(4-(4-pentylcyclohexyl)cyclohexyl)-1,2-difluorobenzene                                                    6%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           7%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)propylbenzene                                                           7%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methoxybenzene                                                          7%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)-2-fluorobenzonitrile                                                    3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)-2-fluorobenzonitrile                                                   7%                                                2-4'-fluorobiphenyl-5-propylpyrimidine                                                                      3%                                                2-4'-fluorobiphenyl-5-butylpyrimidine                                                                       3%                                                2-(4-fluorophenyl)-5-pentylpyrimidine                                                                       3%                                                Composition Example 5                                                          4'-(4-(1,5-hexadienyl)cyclohexyl)-4-ethylbiphenyl                                                           7%                                                4-(4-(1,5-hexadienyl)cyclohexyl)benzonitrile                                                                8%                                                4-(4-(3-butenyl)cyclohexyl)benzonitrile                                                                    10%                                                4-(4-(3-pentenyl)cyclohexyl)benzonitrile                                                                   10%                                                4-(4-propylcyclohexyl)benzonitrile                                                                         20%                                                4-(4-pentylcyclohexyl)benzonitrile                                                                         20%                                                2-(4-ethylphenyl)-5-ethylpyrimidine                                                                         3%                                                2-(4-ethylphenyl)-5-propylpyrimidine                                                                        3%                                                2-(4-ethylphenyl)-5-butylpyrimidine                                                                         3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           5%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)propylbenzene                                                           5%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methoxybenzene                                                          3%                                                4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethenyl)                                                        3%                                                ethylbenzene                                                                   2-(4-(4-propylcyclohexyl)phenyl)-5-ethylpyrimidine                                                          2%                                                2-(4-(4-propylcyclohexyl)phenyl)-5-propylpyrimidine                                                         2%                                                2-(4'-fluorobiphenyl)-5-ethylpyrimidine                                                                     2%                                                2-(4-cyanophenyl)-5-ethyl-1,3-dioxane                                                                       2%                                                2-(4-cyanophenyl)-5-propyl-1,3-dioxane                                                                      2%                                                Composition Example 6                                                          4'-(1,5-hexadienyl)-4-methylbicyclohexane                                                                   5%                                                4'-(1,5-hexadienyl)-4-ethylbicyclohexane                                                                    5%                                                4-(4-(1,5-hexadienyl)cyclohexyl)benzonitrile                                                               10%                                                4-(4-(3-butenyl)cyclohexyl)benzonitrile                                                                     8%                                                4-(4-(3-pentenyl)cyclohexyl)benzonitrile                                                                    8%                                                4-(4-propylcyclohexyl)benzonitrile                                                                          8%                                                4-(4-pentylcyclohexyl)benzonitrile                                                                          8%                                                4-(4-methoxymethylcyclohexyl)benzonitrile                                                                   8%                                                4-(4-ethoxymethylcyclohexyl)benzonitrile                                                                    4%                                                4-(2-(4-ethylphenyl)ethynyl)methoxybenzene                                                                  2%                                                4-(2-(4-propylphenyl)ethynyl)methoxybenzene                                                                 2%                                                4-(2-(4-butylphenyl)ethynyl)methoxybenzene                                                                  2%                                                4-(2-(4-pentylphenyl)ethynyl)methoxybenzene                                                                 2%                                                4-(2-(4-butylphenyl)ethynyl)ethoxybenzene                                                                   2%                                                4'-propyl-4-butylbicyclohexane                                                                              8%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)benzonitrile                                                             4%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)benzonitrile                                                            4%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           5%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)propylbenzene                                                           5%                                                Composition Example 7                                                          4-(4-(1,5-hexadienyl)cyclohexyl)benzonitrile                                                               10%                                                4-(4-(1,5-hexadienyl)cyclohexyl)propylbenzene                                                               5%                                                4'-(1,5-hexadienyl)-4-propylbicyclohexane                                                                   5%                                                4-(4-ethylphenyl)benzonitrile                                                                               6%                                                4-(4-butylphenyl)benzonitrile                                                                               6%                                                4-(4-pentylphenyl)benzonitrile                                                                              6%                                                4-(4-ethylcyclohexyl)benzonitrile                                                                          10%                                                4-(4-propylcyclohexyl)benzonitrile                                                                          5%                                                2-(4-butylphenyl)-5-propylpyrimidine                                                                        1.5%                                              2-(4-butylphenyl)-5-butylpyrimidine                                                                         1.5%                                              2-(4-butylphenyl)-5-pentylpyrimidine                                                                        1.5%                                              2-(4-pentylphenyl)-5-propylpyrimidine                                                                       1.5%                                              2-(4-pentylphenyl)-5-butylpyrimidine                                                                        1.5%                                              2-(4-pentylphenyl)-5-hexylpyrimidine                                                                        1.5%                                              4-(4-(4-ethylcyclohexyl)cyclohexyl)methylbenzene                                                            3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           5%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)propylbenzene                                                           8%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methoxybenzene                                                          3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)fluorobenzene                                                           3%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)benzonitrile                                                             4%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)benzonitrile                                                            4%                                                4-(4-(4-butylcyclohexyl)cyclohexyl)benzonitrile                                                             4%                                                2-(4-methoxyphenyl)-5-ethylpyrimidine                                                                       2%                                                2-(4-ethoxyphenyl)-5-propylpyrimidine                                                                       2%                                                Composition Example 8                                                          4'-(1,5-heptadienyl)-4-propylbicyclohexane                                                                  3%                                                4-(2-(4-(1,5-hexadienyl)cyclohexyl)ethyl)propyl-                                                            3%                                                cyclohexane                                                                    4-(4-(1,5-hexadienyl)cyclohexyl)benzonitrile                                                               10%                                                4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                              3%                                                benzonitrile                                                                   3-fluoro-4-cyanophenyl-4-ethoxymethylbenzoate                                                               3%                                                3-fluoro-4-cyanophenyl-4-propoxymethylbenzoate                                                              3%                                                4-(4-methoxymethylcyclohexyl)benzonitrile                                                                   5%                                                4-(4-ethylcyclohexyl)benzonitrile                                                                          20%                                                4-(4-propylcyclohexyl)benzonitrile                                                                         15%                                                4'-methoxymethyl-4-pentylbicyclohexane                                                                      8%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)benzonitrile                                                             3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)benzonitrile                                                            3%                                                4-(4-(4-butylcyclohexyl)cyclohexyl)benzonitrile                                                             3%                                                2-(4'-fluorobiphenyl)-5-propylpyrimidine                                                                    3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           3%                                                4-fluorophenyl-4-(4-propylcyclohexyl)cyclohexane-                                                           3%                                                carboxylate                                                                    4-fluorophenyl-4-(4-pentylcyclohexyl)cyclohexane-                                                           3%                                                carboxylate                                                                    2-(4'-ethylbiphenyl)-5-propylpryimidine                                                                     3%                                                2-(4'-butylbiphenyl)-5-propylpyrimidine                                                                     3%                                                Composition Example 9                                                          4-(4-(2-(4-(1,6-heptadienyl)cyclohexyl)ethyl)                                                               9%                                                cyclohexyl)-1,2-difluorobenzene                                                4-(2-(4-(1,7-octadienyl)phenyl)ethynyl)pentylbenzene                                                        9%                                                4-(4-(1,5-hexadienyl)cyclohexyl)benzonitrile                                                                3%                                                4-(4-propylcyclohexyl)benzonitrile                                                                         10%                                                4-(4-propoxylmethylcyclohexyl)benzonitrile                                                                  8%                                                4-(2-(4-ethylphenyl)ethynyl)methylbenzene                                                                   4%                                                4-(2-(4-propylphenyl)ethynyl)hexylbenzene                                                                   8%                                                4-(2-(4-butylphenyl)ethynyl)butylbenzene                                                                    4%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)benzonitrile                                                            3%                                                4-(4-(2-(4-ethylcyclohexyl)ethyl)cyclohexyl)-1,2-                                                          10%                                                difluorobenzene                                                                4-(4-(2-(4-propylcyclohexyl)ethyl)cyclohexyl)-1,2-                                                          5%                                                difluorobenzene                                                                4-(4-(2-(4-pentylcyclohexyl)ethyl)cyclohexyl)-1,2-                                                         10%                                                difluorobenzene                                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methoxybenzene                                                          3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           7%                                                4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)                                                        3%                                                ethylbenzene                                                                   Composition Example 10                                                         4-(1,5-hexadienyl)phenyl-4-(4-propylcyclohexyl)benzoate                                                    10%                                                4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                              6%                                                propylbenzene                                                                  4'-(3,7-octadienyl)-4-propylbicyclohexane                                                                   6%                                                4-(4-ethylcyclohexyl)-2-fluorobenzonitrile                                                                  3%                                                4-(4-propylcyclohexyl)-2-fluorobenzonitrile                                                                 3%                                                4-(4-pentylcyclohexyl)-2-fluorobenzonitrile                                                                 3%                                                4-ethylphenyl-4-methoxybenzoate                                                                             5%                                                4-fluorophenyl-4-pentylcyclohexanecarboxylate                                                               4%                                                4-fluorophenyl-4-heptylcyclohexanecarboxylate                                                               4%                                                4-butoxyphenyl-4-propylcyclohexanecarboxylate                                                               8%                                                4-ethoxyphenyl-4-butylcyclohexanecarboxylate                                                                6%                                                4-methoxyphenyl-4-pentylcyclohexanecarboxylate                                                              6%                                                4-ethoxyphenyl-4-propylcyclohexanecarboxylate                                                               5%                                                4-ethoxyphenyl-4-pentylcyclohexanecarboxylate                                                               4%                                                4-ethoxyphenyl-4-butylcyclohexanecarboxylate                                                                8%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           5%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)propylbenzene                                                           5%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methoxybenzene                                                          3%                                                4-fluorophenyl-4-(4-propylcyclohexanoyloxy)benzoate                                                         3%                                                Composition Example 11                                                         2-(4-(1,5-hexadienyl)phenyl)-5-propylpyrimidine                                                             5%                                                4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                              5%                                                methylbenzene                                                                  4-(1,5-hexadienyl)phenyl-4-(4-propylcyclohexyl)benzoate                                                     5%                                                2-(3,4-difluorophenyl)-5-propylpyrimidine                                                                   8%                                                2-(4'-fluorobiphenyl)-5-propylpyrimidine                                                                    5%                                                2-(4'-fluorobiphenyl)-5-butylpyrimidine                                                                     5%                                                2-(4'-fluorobiphenyl)-5-pentylpyrimidine                                                                    5%                                                2-(4-ethylphenyl)-5-ethylpyrimidine                                                                         4%                                                2-(4-ethylphenyl)-5-propylpyrimidine                                                                        4%                                                2-(4-ethylphenyl)-5-butylpyrimidine                                                                         4%                                                4-butoxyphenyl-4-propylcyclohexanecarboxylate                                                               6%                                                4-ethoxyphenyl-4-butoxycyclohexanecarboxylate                                                               6%                                                4-ethoxyphenyl-4-pentylcyclohexanecarboxylate                                                               6%                                                4-(2-(4-(2-(4-ethylcyclohexyl)ethyl)phenyl)ethynyl)                                                         4%                                                butylbenzene                                                                   4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethynyl)                                                        4%                                                butylbenzene                                                                   4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           6%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)propylbenzene                                                           6%                                                4'-cyanobiphenyl-4-(4-propylcyclohexyl)cyclohexane-                                                         3%                                                carboxylate                                                                    4'-cyanobiphenyl-4-(4-pentylcyclohexyl)cyclohexane-                                                         3%                                                carboxylate                                                                    4'-cyanobiphenyl-4-(4-propylcyclohexyl)benzoate                                                             3%                                                Methyl-4-(4-pentylcyclohexylycyclohexanecarboxylate                                                         3%                                                Composition Example 12                                                         4'-(1,5-hexadienyl)-4-pentylbicyclohexane                                                                   6%                                                4-(4-(1,5-hexadienyl)cyclohexyl)propylbenzene                                                               5%                                                4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                              5%                                                methylbenzene                                                                  4-(4-heptylcyclohexyl)-1,3-difluorobenzene                                                                  4%                                                4-(2-(4-pentylcyclohexyl)ethyl)-1,2-difluorobenzene                                                         5%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)-1,2-difluorobenzene                                                    11%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)-1,2-difluorobenzene                                                   11%                                                4-(4-(4-pentylcyclohexyl)cyclohexyl)-1,2-difluorobenzene                                                   11%                                                4-(4-(2-(4-ethylcyclohexyl)ethyl)cyclohexyl)-1,2-                                                           2%                                                difluorobenzene                                                                4-(4-(2-(4-propylcyclohexyl)ethyl)cyclohexyl)-1,2-                                                          1%                                                difluorobenzene                                                                4-(4-(2-(4-pentylcyclohexyl)ethyl)cyclohexyl)-1,2-                                                          2%                                                difluorobenzene                                                                4'-(4-ethylcyclohexyl)-3,4-difluorobiphenyl                                                                 4%                                                4'-(4-propylcyclohexyl)-3,4-difluorobiphenyl                                                                4%                                                4'-(4-pentylcyclohexyl)-3,4-difluorobiphenyl                                                                8%                                                4'-(4-ethylcyclohexyl)-4-fluorobiphenyl                                                                     3%                                                4'-(4-propylcyclohexyl)-4-fluorobiphenyl                                                                    3%                                                4'-(4-pentylcyclohexyl)-4-fluorobiphenyl                                                                    2%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)fluorobenzene                                                           3%                                                4-(4-(4-propylcyclohexyl)cyclohexyl)methylbenzene                                                           5%                                                4-(2-(4-pentylcyclohexyl)ethyl)-1,2-difluorobenzene                                                         5%                                                Composition Example 13                                                         4'-(4-(1,5-hexadienyl)cyclohexyl)-4-ethylbiphenyl                                                           4%                                                4'-(1,5-hexadienyl)-4-pentylbicyclohexane                                                                   6%                                                4-(4-(1,5-hexadienyl)cyclohexyl)propylbenzene                                                               3%                                                5-(4-heptylcyclohexyl)-1,2,3-trifluorobenzene                                                               8%                                                5-(4-(4-propylcyclohexyl)cyclohexyl)-1,2,3-                                                                 8%                                                trifluorobenzene                                                               5-(4-(4-butylcyclohexyl)cyclohexyl)-1,2,3-                                                                  4%                                                trifluorobenzene                                                               5-(4-(2-(4-propylcyclohexyl)ethyl)cyclohexyl)-1,2,3-                                                       10%                                                trifluorobenzene                                                               5-(4-(2-(4-butylcyclohexyl)ethyl)cyclohexyl)-1,2,3-                                                         8%                                                trifluorobenzene                                                               5-(4-(2-(4-pentylcyclohexyl)ethyl)cyclohexyl)-1,2,3-                                                        8%                                                trifluorobenzene                                                               5-(2-(4-(4-propylcyclohexyl)cyclohexyl)ethyl)-1,2,3-                                                       10%                                                trifluorobenzene                                                               5-(2-(4-(4-pentylcyclohexyl)cyclohexyl)ethyl)-1,2,3-                                                        9%                                                trifluorobenzene                                                               4'-(4-propylcyclohexyl)-3,4,5-trifluorobiphenyl                                                             8%                                                4'-(4-pentylcyclohexyl)-3,4,5-trifluorobiphenyl                                                             8%                                                4'-(4-(4-propylcyclohexyl)cyclohexyl)-3,4,5-                                                                3%                                                trifluorobiphenyl                                                              4'-(2-(4-(4-propylcyclohexyl)cyclohexyl)ethyl)-3,4,5-                                                       3%                                                trifluorobiphenyl                                                              Composition Example 14                                                         4'-(4-(1,5-hexadienyl)cyclohexyl)-3,4,5-                                                                   10%                                                trifluorobiphenyl                                                              4'-(1,5-heptadienyl)-4-propylbicyclohexane                                                                  3%                                                4'-(4-(1,5-hexadienyl)cyclohexyl)-4-(4-propylcyclohexyl)                                                    3%                                                biphenyl                                                                       5-(4-(2-(4-propylcyclohexyl)ethyl)cyclohexyl-1,2,3-                                                         7%                                                trifluorobenzene                                                               5-(4-(2-(4-butylcyclohexyl)ethyl)cyclohexyl-1,2,3-                                                          7%                                                trifluorobenzene                                                               5-(4-(2-(4-pentylcyclohexyl)ethyl)cyclohexyl-1,2,3-                                                         6%                                                trifluorobenzene                                                               5-(2-(4-(4-propylcyclohexyl)cyclohexyl)ethyl)-1,2,3-                                                        5%                                                trifluorobenzene                                                               4'-(2-(4-propylcyclohexyl)ethyl)-3,4,5-trifluorobiphenyl                                                    5%                                                4'-(2-(4-butylcyclohexyl)ethyl)-3,4,5-trifluorobiphenyl                                                     5%                                                4'-(2-(4-pentylcyclohexyl)ethyl)-3,4,5-trifluorobiphenyl                                                    5%                                                3,4,5-trifluorophenyl-4-(4-propylcyclohexyl)benzoate                                                        2%                                                3,4,5-trifluorophenyl-4-(4-pentylcyclohexyl)benzoate                                                        2%                                                3,4,5-trifluorophenyl-4-(4-propylcyclohexyl)                                                                8%                                                cyclohexanecarboxylate                                                         Composition Example 15                                                         4'-(4-(1,5-hexadienyl)cyclohexyl)-3,4,5-trifluorobiphenyl                                                   7%                                                4-(2-(4-(1,5-hexadienyl)cyclohexyl)ethenyl)                                                                 7%                                                propylcyclohexane                                                              4-(4-(4-(6,6-difluoro-1,5-hexadienyl)cyclohexyl)                                                            7%                                                cyclohexyl)pentylcyclohexane                                                   4-(4-propylcyclohexyl)chlorobenzene                                                                         5%                                                5-(4-heptylcyclohexyl)-3,4,5-trifluorobenzene                                                               8%                                                4'-(4-ethylcyclohexyl)-3,4-difluorobiphenyl                                                                 6%                                                4'-(4-propylcyclohexyl)-3,4-difluorobiphenyl                                                                6%                                                4'-(4-pentylcyclohexyl)-3,4-difluorobiphenyl                                                                6%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)chlorobenzene                                                            4%                                                4-(4-(4-butylcyclohexyl)cyclohexyl)chlorobenzene                                                            8%                                                4-(4-(4-pentylcyclohexyl)cyclohexyl)chlorobenzene                                                           4%                                                4'-(4-propylcyclohexyl)-3,4,5-trifluorobiphenyl                                                            10%                                                4'-(4-pentylcyclohexyl)-3,4,5-trifluorobiphenyl                                                            10%                                                4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethenyl)                                                        4%                                                ethylbenzene                                                                   4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethenyl)                                                        4%                                                propylbenzene                                                                  4-(4-(2-(4-propylcyclohexyl)ethyl)cyclohexyl)-3-                                                            4%                                                fluorochlorobenzene                                                            Composition Example 16                                                         4'-(1,5-hexadienyl)-4-propylbicyclohexane                                                                   7%                                                4'-(1,5-hexadienyl)-4-pentylbicyclohexane                                                                   7%                                                4'-(4-(1,5-hexadienyl)cyclohexyl-3,4,5-trifluorobenzene                                                     7%                                                4-(4-pentylcyclohexyl)fluorobenzene                                                                         8%                                                4-(4-heptylcyclohexyl)fluorobenzene                                                                         8%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)trifluoro-                                                               5%                                                methoxybenzene                                                                 4-(4-(4-propylcyclohexyl)cyclohexyl)trifluoro-                                                              5%                                                methoxybenzene                                                                 4-(4-(4-pentylcyclohexyl)cyclohexyl)trifluoro-                                                              5%                                                methoxybenzene                                                                 1,6-difluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)                                                          15%                                                difluoromethoxybenzene                                                         1,6-difluoro-4-(4-(4-pentylcyclohexyl)cyclohexyl)                                                          15%                                                difluoromethoxybenzene                                                         2',6'-difluoro-4'-(propylcyclohexyl)-3,4-                                                                   6%                                                difluorobiphenyl                                                               2',6'-difluoro-4'-(pentylcyclohexyl)-3,4-                                                                   6%                                                difluorobiphenyl                                                               4-trifluoromethoxyphenyl-4-(4-propylcyclohexyl)                                                             3%                                                cyclohexanecarboxylate                                                         4-trifluoromethoxyphenyl-4-(4-pentylcyclohexyl)                                                             3%                                                cyclohexanecarboxylate                                                         Composition Example 17                                                         4'-(4-(1,5-hexadienyl)cyclohexyl)-3,4,5-                                                                   10%                                                trifluorobiphenyl                                                              4-(4-(2-(4-(1,6-heptadienyl)cyclohexyl)ethyl)                                                              10%                                                cyclohexyl)-3,4-difluorobenzene                                                4-(4-pentylcyclohexyl)fluorobenzene                                                                         8%                                                4-(4-hexylcyclohexyl)fluorobenzene                                                                          8%                                                4-(4-heptylcyclohexyl)fluorobenzene                                                                         8%                                                4-(4-(4-ethylcyclohexyl)cyclohexyl)trifluoro-                                                               6%                                                methoxybenzene                                                                 4-(4-(4-propylcyclohexyl)cyclohexyl)trifluoro-                                                              6%                                                methoxybenzene                                                                 4-(4-(4-butylcyclohexyl)cyclohexyl)trifluoro-                                                               6%                                                methoxybenzene                                                                 4-(4-(4-pentylcyclohexyl)cyclohexyl)trifluoro-                                                              6%                                                methoxybenzene                                                                 4-(2-(4-(4-propylcyclohexyl)cyclohexyl)ethyl)                                                               5%                                                trifluoromethylbenzene                                                         4-(2-(4-(4-pentylcyclohexyl)cyclohexyl)ethyl)                                                               5%                                                trifluoromethylbenzene                                                         4'-(4-propylcyclohexyl)-3,4-difluorobiphenyl                                                                8%                                                4'-(4-pentylcyclohexyl-3,4-difluorobiphenyl                                                                 8%                                                2'-fluoro-4'-(4-propylcyclohexyl)-4-(4-propylcyclohexyl)                                                    3%                                                biphenyl                                                                       2'-fluoro-4'-(4-pentylcyclohexyl)-4-(4-propylcyclohexyl)                                                    3%                                                biphenyl                                                                       Composition Example 18                                                         4-(4-(1,5-hexadienyl)cyclohexyl)benzonitrile                                                                5%                                                4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                              5%                                                benzonitrile                                                                   4'-(1,5-hexadienyl)-4-methylbicyclohexane                                                                   5%                                                4-(4-(4-(1,5-hexadienyl)cyclohexyl)cyclohexyl)                                                              5%                                                propylbenzene                                                                  4-(4-(2-propenyl)cyclohexyl)benzonitrile                                                                    4%                                                4'-butyl-4-ethylbiphenyl     4%                                                4'-propyl-4-cyanobiphenyl    5%                                                4'-pentyl-4-cyanobiphenyl    5%                                                2-fluoro-4-(4-ethylcyclohexyl)benzonitrile                                                                  5%                                                4-(2-(4-propylcyclohexyl)ethyl)ethoxybenzene                                                                5%                                                4-(2-(4-pentylcyclohexyl)ethyl)propoxybenzene                                                               8%                                                4'-pentyl-4-cyanobiphenyl    3%                                                2-(4-cyanophenyl)-5-(4-butylphenyl)pyrimidine                                                               3%                                                2-(4-pentylphenyl)-5-(4-butylphenyl)pyrimidine                                                              3%                                                4-(2-(4-(4-pentylcyclohexyl)phenyl)ethyl)butylbenzene                                                       3%                                                4-(2-(4-propylphenyl)ethyl)-4'-(4-pentylcyclohexyl)                                                         3%                                                biphenyl                                                                       4'-(1-propenyl)-4-methoxymethylbicyclohexane                                                                5%                                                4'-propyl-4-(4-(3-pentenyl)cyclohexyl)biphenyl                                                              5%                                                4-cyanophenyl-4-propylbenzoate                                                                              5%                                                4-methoxyphenyl-4-pentylcyclohexanecarboxylate                                                              7%                                                4-propoxyphenyl-4-pentylcyclohexanecarboxylate                                                              7%                                                Composition Example 19                                                         4-(4-(2-(4-(1,6-heptadienyl)cyclohexyl)ethyl)                                                              10%                                                cyclohexyl)-3,4-difluorobenzene                                                4-(2-(4-(1,7-octadienyl)phenyl)ethynyl)pentylbenzene                                                       10%                                                3,4-difluorophenyl-4-butylcyclohexanecarboxylate                                                            5%                                                3,4-difluorophenyl-4-pentylcyclohexanecarboxylate                                                           5%                                                3-fluoro-4-cyanophenyl-4-ethylbenzoate                                                                      4%                                                3-fluoro-4-cyanophenyl-4-propylbenzoate                                                                     4%                                                3-fluoro-4-cyanophenyl-4-butylbenzoate                                                                      6%                                                3-fluoro-4-cyanophenyl-4-pentylbenzoate                                                                     6%                                                2-fluoro-4-(4-(3-methoxypropyl)cyclohexyl)benzonitrile                                                      6%                                                3,4-difluorophenyl-4-(4-propylcyclohexyl)                                                                   4%                                                cyclohexanecarboxylate                                                         3,4-difluorophenyl-4-(4-pentylcyclohexyl)                                                                   4%                                                cyclohexanecarboxylate                                                         3-fluoro-4-cyanophenyl-4-(4-ethylcyclohexyl)benzoate                                                        5%                                                3-fluoro-4-cyanophenyl-4-(4-propylcyclohexyl)benzoate                                                       5%                                                3-fluoro-4-cyanophenyl-4-(4-butylcyclohexyl)benzoate                                                        5%                                                3-fluoro-4-cyanophenyl-4-(4-pentylcyclohexyl)benzoate                                                       5%                                                4-(2-(4-(4-propylcyclohexyl)phenyl)ethynyl)ethylbenzene                                                    10%                                                4'-(3-butenyl-4-propylbicyclohexane                                                                         3%                                                4-(4-(4-(3-butenyl)cyclohexyl)cyclohexyl)methylbenzene                                                      3%                                                ______________________________________                                    

Compounds of the present invention exhibit a large ratio of elastic constants K₃₃ /K₁₁ and an extremely low viscosity. As shown in the Examples (Use Examples) mentioned below, the compounds of the present invention have about the same extent of a large elastic constant ratio K₃₃ /K₁₁ as that of the alkenyl compounds which are currently most widely used, have a large elastic constant ratio K₃₃ /K₁₁ and a low viscosity, and described in Laid-open Japanese Patent Publication No. Sho 61-83136 and Laid-open Japanese Patent Publication No. Sho 61-56137; and the compounds of the-present invention exhibit a lower viscosity than that of the alkenyl compounds.

    __________________________________________________________________________      ##STR17##                 K33/K11 = 1.78                                                                         Extrapolated viscosity 17.8 mPa                                                · s                                 ##STR18##                 K33/K11 = 2.02                                                                         Extrapolated viscosity 15.0 mPa                                                · s                                __________________________________________________________________________

Compounds of Example 1

Further, the compounds of the present invention exhibit a high stability as shown in Examples and have a chemical stability sufficient to be used for practical liquid crystal compositions.

By using the compounds (1) of the present invention having excellent characteristics, liquid crystal compositions having such excellent physical properties, that is, steep threshold characteristics and high response speed can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION

Methods for preparing and using the compounds of the present invention are described in more detail in the following with reference to Examples. In each of the Examples, Cr represents crystal, N does nematic phase, S does smectic phase, and Iso represents isotropic liquid, and all of the unit of phase transition temperature is ° C.

EXAMPLE 1

Preparation of 4-(4-(1,5-hexedienyl)cyclohexyl)-1-pentylcycl ohexane ##STR19## (Compound No. 8 expressed by general formula (1) in which R₁ represents pentyl group, X₃ represents a covalent bond, C and D represent trans-1,4-cyclohexane ring, l, m, and n are 0, o is 1, p is 2,. and R₂ and R₂ ' are hydrogen atom.)

A mixture of a commercially available 1-bromo-5-pentene (600 mmol), triphenylphosphine (500 mmol), and 300 ml of toluene was heated to reflux for 40 hours. White crystals thus precipitated were filtered off, washed with toluene thrice, and then dried under a reduced pressure to obtain a phosphonium salt (500 mmol).

Potassium-t-butoxide (550 mmol) was added to the mixture of the phosphonium salt mentioned above (500 mmol) and 500 ml of tetrahydrofuran (hereinafter referred to as THF), and stirred at room temperature for 2 hours. To the red solution thus obtained was added a solution of 4-(4-pentylcyclohexyl)cyclohexane-carboaldehyde (500 mmol) prepared according to the method of Laid-open Japanese Patent Publication No. Sho 61-83136 in 300 ml of THF at a temperature lower than 0° C., and stirred at room temperature for 4 hours. It was put in 500 ml of water and extracted with 500 ml of toluene, and the organic-layer was washed with 2M hydrochloric acid and saturated aqueous solution of sodium bicarbonate, and then washed with water until it became neutral. After it was dried with anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified with a silica gel column chromatography (eluent:heptane) to obtain 4-(4-(cis-1,5-hexedienyl)cyclohexyl)-1-PENTYLCYCLOHEXANE (250 mmol).

m-Chloroperbenzoic acid (750 mmol) and potassium carbonate (1.5 mol) were added to the solution of the compound mentioned above (250 mmol) in 200 ml of methylene chloride and stirred at room temperature for 8 hours. After 500 ml of saturated aqueous solution of sodium thiosulfate was added to the reaction solution and stirred, the organic layer was washed with water thrice and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure to obtain 4-(4-(cis-1,5-hexedienyl)cyclohexyl)-1-pentyl-cyclohexanedioxide (200 mmol).

Mixture of the epoxide compound mentioned above (200 mmol), triphenylphosphine dibromide (600 mmol), and 200 ml of toluene was stirred under a heated condition for 3 hours. After cooled down, the reaction solution was put in 300 ml of water and extracted with 300 ml of toluene, and the organic layer was washed with 2M hydrochloric acid and saturated aqueous solution of sodium bicarbonate, and then washed with water until it became neutral. After it was dried with anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column chromatography (eluent:toluene) and recrystallized by using ethanol 5 times as much as the residue to obtain 100 mmol of 4-(4-(1,2,5,6-tetrabromohexyl) cyclohexyl)-1-pentylcyclohexane.

Mixture of the bromide mentioned above (100 mmol), 800 mmol of metal zinc, and 20 ml of acetic acid was stirred at room temperature for 12 hours. Water in an amount of 100 ml was added, extracted with 50 ml of toluene, and the organic layer was washed with 2N hydrochloric acid and saturated aqueous solution of sodium bicarbonate and then washed with water until it became neutral. After it was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column chromatography (eluent:heptane) and recrystallized twice from ethanol/heptane (1/1) mixed solvent 5 times as much as the residue to obtain 80 mmol of the subject compound. This compound showed smectic at room temperature and had a clearing point of 107.1 to 107.6° C. Also, NMR spectrum, mass spectrum, IR spectrum, and the values of elementary analysis of this compound well supported its structure.

According to the method of Example 1, the following compounds were prepared:

       - R1 A X1 B X2 C X3 D W       1 CH3      ##STR20##       ##STR21##       ##STR22##       S 28.1 Iso        2 C2H5       ##STR23##       ##STR24##       ##STR25##       S 64.1 Iso        3 C3H7       ##STR26##       ##STR27##       ##STR28##       S 86.2 N 88.6 Iso        4 C3H7       ##STR29##       ##STR30##       ##STR31##        5 C3H7       ##STR32##       ##STR33##       ##STR34##        6 C3H7       ##STR35##       ##STR36##       ##STR37##        7 C4H9       ##STR38##       ##STR39##       ##STR40##       S 97.9 Iso        8 C5H11       ##STR41##       ##STR42##       ##STR43##       S 107.6 Iso        9 C3H7       ##STR44##       CH2CH2       ##STR45##       ##STR46##       S 88.2 Iso        10 C5H11       ##STR47##       CH2CH2       ##STR48##       ##STR49##        11 C3H7       ##STR50##       (CH2)4       ##STR51##       ##STR52##        12 C5H11       ##STR53##       (CH2)4       ##STR54##       ##STR55##        13 C3H7       ##STR56##       ##STR57##       ##STR58##       Cr -18.8 Iso        14 C3H7       ##STR59##       ##STR60##       ##STR61##        15 C3H7       ##STR62##       ##STR63##       ##STR64##        16 NC       ##STR65##       ##STR66##       ##STR67##       S 56.2 N 67.0 Iso        17 NC       ##STR68##       ##STR69##       ##STR70##        18 F       ##STR71##       ##STR72##       ##STR73##        19 F       ##STR74##       ##STR75##       ##STR76##        20 C3H7       ##STR77##       CH2CH2       ##STR78##       ##STR79##        21 NC       ##STR80##       CH2CH2       ##STR81##       ##STR82##        22 NC       ##STR83##       CH2CH2       ##STR84##       ##STR85##        23 F       ##STR86##       CH2CH2       ##STR87##       ##STR88##        24 F       ##STR89##       CH2CH2       ##STR90##       ##STR91##        25 C3H7       ##STR92##       ##STR93##       ##STR94##        26 NC       ##STR95##       ##STR96##       ##STR97##        27 NC       ##STR98##       ##STR99##       ##STR100##        28 NC       ##STR101##       ##STR102##       ##STR103##        29 NC       ##STR104##       ##STR105##       ##STR106##        30 NC       ##STR107##       ##STR108##       ##STR109##        31 C3H7       ##STR110##       ##STR111##       ##STR112##       ##STR113##        32 C5H11       ##STR114##       ##STR115##       ##STR116##       ##STR117##        33 C3H7       ##STR118##       ##STR119##       ##STR120##       ##STR121##        34 C5H11       ##STR122##       CH2CH2       ##STR123##       ##STR124##       ##STR125##        35 NC       ##STR126##       CH2CH2       ##STR127##       ##STR128##       ##STR129##        36 F       ##STR130##       CH2CH2       ##STR131##       ##STR132##       ##STR133##        37 NC       ##STR134##       CH2CH2       ##STR135##       ##STR136##       ##STR137##        38 NC       ##STR138##       CH2CH2       ##STR139##       ##STR140##       ##STR141##        39 C3H7       ##STR142##       CH2CH2       ##STR143##       CH2CH2       ##STR144##       ##STR145##        40 C4H9       ##STR146##       CH2CH2       ##STR147##       CH2CH2       ##STR148##       ##STR149##        41 C5H11       ##STR150##       CH2CH2       ##STR151##       CH2CH2       ##STR152##       ##STR153##        42 NC       ##STR154##       CH2CH2       ##STR155##       CH2CH2       ##STR156##       ##STR157##        43 NC       ##STR158##       CH2CH2       ##STR159##       CH2CH2       ##STR160##       ##STR161##        44 C3H7       ##STR162##       ##STR163##       CH2CH2       ##STR164##       ##STR165##        45 C3H7       ##STR166##       ##STR167##       CH2CH2       ##STR168##       ##STR169##        46 C4H9       ##STR170##       ##STR171##       CH2CH2       ##STR172##       ##STR173##        47 C5H11       ##STR174##       ##STR175##       CH2CH2       ##STR176##       ##STR177##        48 C7H15       ##STR178##       ##STR179##       CH2CH2       ##STR180##       ##STR181##        49 F       ##STR182##       ##STR183##       CH2CH2       ##STR184##       ##STR185##        50 F       ##STR186##       ##STR187##       CH2CH2       ##STR188##       ##STR189##        51 NC       ##STR190##       ##STR191##       CH2CH2       ##STR192##       ##STR193##        52 NC       ##STR194##       ##STR195##       CH2CH2       ##STR196##       ##STR197##        53 NC       ##STR198##       ##STR199##       CH2CH2       ##STR200##       ##STR201##        54 NC       ##STR202##       ##STR203##       CH2CH2       ##STR204##       ##STR205##        55 C3H7       ##STR206##       ##STR207##       (CH2)4       ##STR208##       ##STR209##        56 C4H9       ##STR210##       ##STR211##       (CH2)4       ##STR212##       ##STR213##        57 C5H11       ##STR214##       ##STR215##       (CH2)4       ##STR216##       ##STR217##        58 CH3       ##STR218##       ##STR219##       ##STR220##       ##STR221##        59 CH3       ##STR222##       ##STR223##       ##STR224##       ##STR225##        60 CH3       ##STR226##       ##STR227##       ##STR228##       ##STR229##        61 CH3       ##STR230##       ##STR231##       ##STR232##       ##STR233##        62 C2H5       ##STR234##       ##STR235##       ##STR236##       ##STR237##       S 161.5 Iso        63 C3H7       ##STR238##       ##STR239##       ##STR240##       ##STR241##        64 C4H9       ##STR242##       ##STR243##       ##STR244##       ##STR245##        65 C5H11       ##STR246##       ##STR247##       ##STR248##       ##STR249##        66 F       ##STR250##       ##STR251##       ##STR252##       ##STR253##        67 NC       ##STR254##       ##STR255##       ##STR256##       ##STR257##       122.5 S 129.2 N 209.7 Iso        68 Cl       ##STR258##       ##STR259##       ##STR260##       ##STR261##        69 Cl       ##STR262##       ##STR263##       ##STR264##       ##STR265##        70 F       ##STR266##       ##STR267##       ##STR268##       ##STR269##        71 F       ##STR270##       ##STR271##       ##STR272##       ##STR273##        72 F       ##STR274##       ##STR275##       ##STR276##       ##STR277##        73 CH3       ##STR278##       ##STR279##       CH2CH2       ##STR280##       ##STR281##        74 C2H5       ##STR282##       ##STR283##       CH2CH2       ##STR284##       ##STR285##        75 C3H7       ##STR286##       ##STR287##       CH2CH2       ##STR288##       ##STR289##        76 F       ##STR290##       ##STR291##       CH2CH2       ##STR292##       ##STR293##        77 NC       ##STR294##       ##STR295##       CH2CH2       ##STR296##       ##STR297##        78 NC       ##STR298##       ##STR299##       CH2CH2       ##STR300##       ##STR301##        79       ##STR302##       ##STR303##       (CH2)4       ##STR304##       ##STR305##        80 C5H11       ##STR306##       ##STR307##       (CH2)4       ##STR308##       ##STR309##        81 C3H7       ##STR310##       ##STR311##       ##STR312##       ##STR313##        82 F       ##STR314##       ##STR315##       ##STR316##       ##STR317##        83 C3H7       ##STR318##       ##STR319##       CH2CH2       ##STR320##       ##STR321##        84 C5H11       ##STR322##       ##STR323##       CH2CH2       ##STR324##       ##STR325##        85 C5H11       ##STR326##       ##STR327##       CH2CH2       ##STR328##       ##STR329##        86 C5H11       ##STR330##       ##STR331##       CH2CH2       ##STR332##       ##STR333##        87 C5H11       ##STR334##       ##STR335##       CH2CH2       ##STR336##       ##STR337##        88 C2H5       ##STR338##       CH2CH2       ##STR339##       CH2CH2       ##STR340##       ##STR341##        89 C3H7       ##STR342##       CH2CH2       ##STR343##       CH2CH2       ##STR344##       ##STR345##        90 C4H9       ##STR346##       CH2CH2       ##STR347##       CH2CH2       ##STR348##       ##STR349##        91 C5H11       ##STR350##       CH2CH2       ##STR351##       CH2CH2       ##STR352##       ##STR353##        92 C9H19       ##STR354##       CH2CH2       ##STR355##       CH2CH2       ##STR356##       ##STR357##        93 C3H7       ##STR358##       ##STR359##       (CH2)4       ##STR360##       ##STR361##        94 C5H11       ##STR362##       ##STR363##       (CH2)4       ##STR364##       ##STR365##        95 C3H7       ##STR366##       ##STR367##       (CH2)4       ##STR368##       ##STR369##        96 C3H7       ##STR370##       ##STR371##       (CH2)4       ##STR372##       ##STR373##        97 C3H7       ##STR374##       ##STR375##       ##STR376##       ##STR377##        98 C3H7       ##STR378##       ##STR379##       ##STR380##       ##STR381##        99 C3H7       ##STR382##       ##STR383##       ##STR384##       ##STR385##      100 C3H7       ##STR386##       ##STR387##       ##STR388##       ##STR389##      101 C3H7       ##STR390##       ##STR391##       ##STR392##       ##STR393##      102 C5H11       ##STR394##       ##STR395##       ##STR396##       ##STR397##      103 C3H7       ##STR398##       CH2CH2       ##STR399##       ##STR400##       ##STR401##      104 C4H9       ##STR402##       CH2CH2       ##STR403##       ##STR404##       ##STR405##      105 C5H11       ##STR406##       CH2CH2       ##STR407##       ##STR408##       ##STR409##      106 C2H5       ##STR410##       ##STR411##       ##STR412##       ##STR413##       ##STR414##      107 CH3OCH2       ##STR415##       ##STR416##       ##STR417##       ##STR418##       ##STR419##      108 F       ##STR420##       ##STR421##       ##STR422##       ##STR423##       ##STR424##      109 NC       ##STR425##       ##STR426##       ##STR427##       ##STR428##       ##STR429##      110 CH3       ##STR430##       ##STR431##       CH2CH2       ##STR432##       ##STR433##       ##STR434##      111 C5H11       ##STR435##       ##STR436##       CH2CH2       ##STR437##       ##STR438##       ##STR439##      112 C5H11       ##STR440##       ##STR441##       CH2CH2       ##STR442##       ##STR443##       ##STR444##      113 C2H5OCH2       ##STR445##       ##STR446##       CH2CH2       ##STR447##       ##STR448##       ##STR449##      114 C2H5OCH2       ##STR450##       ##STR451##       CH2CH2       ##STR452##       ##STR453##       ##STR454##      115 C3H7OCH2       ##STR455##       ##STR456##       CH2CH2       ##STR457##       ##STR458##       ##STR459##      116 F       ##STR460##       ##STR461##       CH2CH2       ##STR462##       ##STR463##       ##STR464##      117 F       ##STR465##       ##STR466##       CH2CH2       ##STR467##       ##STR468##       ##STR469##      118 F       ##STR470##       ##STR471##       CH2CH2       ##STR472##       ##STR473##       ##STR474##      119 F       ##STR475##       ##STR476##       CH2CH2       ##STR477##       ##STR478##       ##STR479##      120 NC       ##STR480##       ##STR481##       CH2CH2       ##STR482##       ##STR483##       ##STR484##      121 C3H7       ##STR485##       ##STR486##       ##STR487##       CH2CH2       ##STR488##       ##STR489##      122 C3H7       ##STR490##       ##STR491##       ##STR492##       CH2CH2       ##STR493##       ##STR494##      123 C3H7       ##STR495##       ##STR496##       ##STR497##       (CH2)4       ##STR498##       ##STR499##      124 C5H11       ##STR500##       ##STR501##       ##STR502##       (CH2)4       ##STR503##       ##STR504##      125 C3H7       ##STR505##       ##STR506##       ##STR507##       ##STR508##       ##STR509##      126 C5H11       ##STR510##       ##STR511##       ##STR512##       ##STR513##       ##STR514##      127 F       ##STR515##       ##STR516##       ##STR517##       ##STR518##       ##STR519##      128 F       ##STR520##       ##STR521##       ##STR522##       ##STR523##       ##STR524##      129 C4H9       ##STR525##       ##STR526##       CH2CH2       ##STR527##       ##STR528##       ##STR529##      130 C5H11       ##STR530##       ##STR531##       CH2CH2       ##STR532##       ##STR533##       ##STR534##      131 CH3       ##STR535##       ##STR536##       ##STR537##       ##STR538##       ##STR539##      132 C3H7       ##STR540##       ##STR541##       ##STR542##       ##STR543##       ##STR544##      133 C3H7       ##STR545##       ##STR546##       ##STR547##       ##STR548##       ##STR549##      134 C3H7       ##STR550##       ##STR551##       ##STR552##       ##STR553##       ##STR554##      135 C3H7       ##STR555##       ##STR556##       ##STR557##       ##STR558##       ##STR559##      136 C3H7       ##STR560##       ##STR561##       ##STR562##       ##STR563##       ##STR564##      137 C3H7       ##STR565##       ##STR566##       ##STR567##       ##STR568##       ##STR569##      138 C5H11       ##STR570##       ##STR571##       ##STR572##       ##STR573##       ##STR574##      139 C5H11       ##STR575##       ##STR576##       ##STR577##       ##STR578##       ##STR579##      140 C5H11       ##STR580##       ##STR581##       ##STR582##       ##STR583##       ##STR584##      141 C5H11       ##STR585##       ##STR586##       ##STR587##       ##STR588##       ##STR589##      142 C2H5OCH2       ##STR590##       ##STR591##       ##STR592##       ##STR593##       ##STR594##      143 C3H7OCH2       ##STR595##       ##STR596##       ##STR597##       ##STR598##       ##STR599##      144 C3H7OCH2       ##STR600##       ##STR601##       ##STR602##       ##STR603##       ##STR604##      145 C3H7       ##STR605##       ##STR606##       ##STR607##       CH2CH2       ##STR608##       ##STR609##      146 C3H7       ##STR610##       ##STR611##       ##STR612##       CH2CH2       ##STR613##       ##STR614##      147 C3H7       ##STR615##       ##STR616##       ##STR617##       ##STR618##       ##STR619##      148 C5H11       ##STR620##       ##STR621##       ##STR622##       ##STR623##       ##STR624##      149 C3H7       ##STR625##       ##STR626##       CH2CH2       ##STR627##       ##STR628##       ##STR629##      150 C5H11       ##STR630##       ##STR631##       CH2CH2       ##STR632##       ##STR633##       ##STR634##      151 C3H7       ##STR635##       CH2CH2       ##STR636##       ##STR637##       ##STR638##       ##STR639##      152 C5H11       ##STR640##       CH2CH2       ##STR641##       ##STR642##       ##STR643##       ##STR644##      153 C3H7       ##STR645##       (CH2)4       ##STR646##       ##STR647##       ##STR648##       ##STR649##      154 C5H11       ##STR650##       (CH2)4       ##STR651##       ##STR652##       ##STR653##       ##STR654##      155 CH3       ##STR655##       ##STR656##       ##STR657##       ##STR658##       ##STR659##      156 C3H7       ##STR660##       ##STR661##       ##STR662##       ##STR663##       ##STR664##      157 C3H7       ##STR665##       ##STR666##       ##STR667##       ##STR668##       ##STR669##      158 C3H7       ##STR670##       ##STR671##       ##STR672##       ##STR673##       ##STR674##      159 C5H11       ##STR675##       ##STR676##       ##STR677##       ##STR678##       ##STR679##      160 C5H11       ##STR680##       ##STR681##       ##STR682##       ##STR683##       ##STR684##      161 C5H11       ##STR685##       ##STR686##       ##STR687##       ##STR688##       ##STR689##      162 C5H11       ##STR690##       ##STR691##       ##STR692##       ##STR693##       ##STR694##      163 C3H7OCH2       ##STR695##       ##STR696##       ##STR697##       ##STR698##       ##STR699##      164 CH3OCH2CH2       ##STR700##       ##STR701##       ##STR702##       ##STR703##       ##STR704##      165 FCH2       ##STR705##       ##STR706##       ##STR707##       ##STR708##       ##STR709##      166 C3H7       ##STR710##       ##STR711##       CH2CH2       ##STR712##       ##STR713##       ##STR714##      167 C3H7       ##STR715##       ##STR716##       CH2CH2       ##STR717##       ##STR718##       ##STR719##      168 C5H11       ##STR720##       ##STR721##       CH2CH2       ##STR722##       ##STR723##       ##STR724##      169 C3H7       ##STR725##       ##STR726##       ##STR727##       S.sub.B 91.6˜91.8 Iso      170 C5H11       ##STR728##       ##STR729##       ##STR730##       S 62.2 Iso      171 C5H11       ##STR731##       ##STR732##       ##STR733##       S 36.0 Iso      172 C5H11       ##STR734##       ##STR735##       ##STR736##       S 109.4 Iso      173 C5H11       ##STR737##       ##STR738##       ##STR739##       S 100.4 Iso      174 C5H11       ##STR740##       ##STR741##       ##STR742##       S 69.4 Iso      175 C5H11       ##STR743##       ##STR744##       ##STR745##       S 36.0 Iso      176 C5H11       ##STR746##       ##STR747##       ##STR748##       S 106 N 114.7 Iso      177 CH3       ##STR749##       ##STR750##       ##STR751##       ##STR752##       S 118.2 Iso      178 F       ##STR753##       ##STR754##       ##STR755##       ##STR756##       Cr 39.3 N 144.9 Iso      179 F       ##STR757##       ##STR758##       ##STR759##       ##STR760##       Cr 90.9 N 117.0 Iso      180 NC       ##STR761##       ##STR762##       ##STR763##       ##STR764##       Cr 75.6 N 257.7 Iso

EXAMPLE 2

Preparation of 4-(2-4-(4-propylphenyl)cyclohexyl)ethenyl)-1-(1,5-hexedienyl)cyclohexane ##STR765## (Compound No. 187 expressed by general formula (1) wherein R₁ represents propyl group, X₂ represents a covalent bond, X₃ represents --CH═CH--, B represents 1,4-phenylene ring, C and D represent trans-1,4-cyclohexane ring, l and n are 0, m and o are 1, p is 2, and R₂ and R₂ ' are hydrogen atom.)

Mixture of methoxymethyltriphenylphosphonium chloride (1 mol), potassium-t-butoxide (1 mol), and 1 l of THF was stirred at room temperature for 2 hours. To this mixture was added dropwise the solution of a commercially available 1,4-dioxy-spiro[4,5]deca-8-one (1 mol) in 500 ml of THF at a temperature lower than 0° C. After stirred at room temperature for 4 hours, it was put in 500 ml of water and extracted with 500 ml of toluene. The organic layer was washed with 2M hydrochloric acid and saturated aqueous solution of sodium bicarbonate, and then washed with water until it became neutral. After dried with anhydrous magnesium sulfate, the solvent was distilled off, and the residue was treated by a silica gel column chromatography (eluent:toluene), and the solvent was distilled off under a reduced pressure. To the residue thus obtained was added 500 ml of 6M hydrochloric acid and 1 l of THF, it was stirred at room temperature for 12 hours, and then the organic layer was washed with water thrice. The solvent was distilled off under a reduced pressure to obtain 870 mmol of 1,4-dioxaspiro[4.5] decane-8-carboaldehyde as residue.

After the 4-(4-propylphenyl)cyclohexanecarboxylic acid prepared according to the method described in U.S. Pat. No. 4,229,315 was subjected to a reduction and halogenation according to the methods of M. J. Jorgensen et al., J. Am. Chem. Soc., 87, 1815 (1965) and O. Kamm et al., Synth. Col. I, 25 (1941), the solution of the 4-(4-propylphenyl)cyclohexylmethyl bromide (950 mmol) thus obtained in 500 ml of THF was added dropwise under reflux to the mixture of metal magnesium (950 mmol) and 50 ml of THF to prepare a Gregnard reagent. To this solution was added dropwise at a temperature lower than 0° C. the solution of the 1,4-dioxaspiro[4,5]decane-8-carboaldehyde (870 mmol) prepared by previous procedures in 500 ml of THF, and further they were stirred at room temperature for 2 hours. Reaction product was brought to a temperature lower than 0° C. again, 500 ml of saturated aqueous solution of amonium chloride was added to the reaction product, and they were stirred for 1 hour and then extracted with 1 l of toluene. After the organic layer was washed with water-thrice and dried over anhydrous magnesium sulfate, the organic solvent was distilled off under a reduced pressure. The residue was dissolved in 1 l of toluene, p-toluenesulfonic acid (40 mmol) was added to the solution, and it was refluxed while removing resulted water for 3 hours. After allowed to cool, the toluene layer was washed with water thrice and the solvent was distilled off under a reduced pressure to obtain 670 mmol of 4-(2-(4-(4-propylphenyl) cyclohexyl)ethenyl)cyclohexanone.

Mixture of methoxymethyltriphenylphosphonium chloride (730 mol), potassium-t-butoxide (730 mol), and 700 ml of THF was stirred at room temperature for 2 hours, and the solution of the 4-(2-(4-(4-propylphenyl)cyclohexyl)ethenyl)cyclohexanone (670 mmol) obtained by the previous procedures in 500 ml of THF was added dropwise to the mixture at a temperature lower than 0° C. After stirred at room temperature for 4 hours, it was put in 500 ml of water and extracted with 500 ml of toluene, and the organic layer was washed with 2M hydrochloric acid and saturated bicarbonate and washed with water until it became neutral. After it was dried with anhydrous magnesium sulfate, the solvent was distilled off, the residue was treated by a silica gel column chromatography (eluent:toluene), and the solvent was distilled off under a reduced pressure. To the residue thus obtained were added 500 ml of 6M hydrochloric acid and 1 l of THF, they were stirred at room temperature for 12 hours, and the organic layer was washed with water thrice. The solvent was distilled off under a reduced pressure, and the residue was purified by a silica gel column chromatography (eluent:toluene) to obtain 4-(2-(4-(4-propylphenyl)cyclohexyl)ethenyl) cyclohexanecarboaldehyde (410 mmol).

The phosphonium salt of 1-bromo-5-pentene obtained in Example 1 was reacted with 410 mmol of the 4-(2-(4-(4-propyl-phenyl)cyclohexyl)ethenyl)cyclohexanecarboaldehyde, and then subjected to an epoxidation, bromination, and reduction according to the methods in Example 1 to obtain 64 mmol of the subject compound. NMR spectrum, mass spectrum, IR spectrum, and the values of elementary analysis of this compound well supported its structure.

According to the method of Example 2, the following compounds were prepared:

    __________________________________________________________________________     R1         A X1                                                                               B      X2                                                                               C      X3   D      W                                   __________________________________________________________________________       181 C3H7                                                                                                                  CHTR766##                                                                    ═CH                                                                          #STR767##                                                                      #STR768##                            - 182 C3H7                                                                                                               CH═CH                                                                      #STR770##                                                                      #STR771##                            - 183 C3H7                                                                                                               CH═CH                                                                      #STR773##                                                                      #STR774##                            - 184 C5H11                                                                                                              CH═CH                                                                      #STR776##                                                                      #STR777##                            - 185 C3H7                                                                                                               CH═CH                                                                      #STR779##                                                                      #STR780##                            - 186 C5H11                                                                                                              CH═CH                                                                      #STR782##                                                                      #STR783##                            - 187 C3H7                                                                                                                STR784##                                                                      CH═CH                                                                      #STR786##                                                                      #STR787##                            - 188 C3H7                                                                                                                STR788##                                                                      CH═CH                                                                      #STR790##                                                                      #STR791##                            - 189 C3H7                                                                                                                STR792##                                                                      CH═CH                                                                      #STR794##                                                                      #STR795##                            - 190 C5H11                                                                                                               STR796##                                                                      CH═CH                                                                      #STR798##                                                                      #STR799##                            - 191 CH3                                                                                                                 STR800##                                                                      CH═CH                                                                      #STR802##                                                                      #STR803##                            - 192 C3H7                                                                                                                STR804##                                                                      CH═CH                                                                      #STR806##                                                                      #STR807##                            - 193 C3H7                                                                                                                STR808##                                                                      CH═CH                                                                      #STR810##                                                                      #STR811##                            - 194 C3H7                                                                                                                STR812##                                                                      CH═CH                                                                      #STR814##                                                                      #STR815##                            - 195 C3H7                                                                                                                STR816##                                                                      CH═CH                                                                      #STR818##                                                                      #STR819##                            - 196 C3H7                                                                                                                STR820##                                                                      CH═CH                                                                      #STR822##                                                                      #STR823##                            - 197 C4H9                                                                                                                STR824##                                                                      CH═CH                                                                      #STR826##                                                                      #STR827##                            - 198 C5H11                                                                                                               STR828##                                                                      CH═CH                                                                      #STR830##                                                                      #STR831##                            - 199 C3H7OCH2                                                                                                            STR832##                                                                      CH═CH                                                                      #STR834##                                                                      #STR835##                            - 200 C5H11OCH2                                                                                                           STR836##                                                                      CH═CH                                                                      #STR838##                                                                      #STR839##                            - 201 CH3OCH2CH2                                                                                                          STR840##                                                                      CH═CH                                                                      #STR842##                                                                      #STR843##                            - 202 CH3OCH2CH2CH2                                                                                                       STR844##                                                                      CH═CH                                                                      #STR846##                                                                      #STR847##                            - 203 FCH2CH2                                                                                                             STR848##                                                                      CH═CH                                                                      #STR850##                                                                      #STR851##                            - 204 FCH2CH2CH2                                                                                                          STR852##                                                                      CH═CH                                                                      #STR854##                                                                     ##STR855##                         __________________________________________________________________________

EXAMPLE 3

Preparation of 4-(2-(4-methylphenyl)ethynyl)-1-(1,5-hexadienyl)benzene ##STR856## (Compound No. 205 expressed by general formula (1) wherein R₁ represents methyl group, X₃ represents --C.tbd.C--, C and D represent trans-1,4-cyclohexane ring, l, m, and n are 0, o is 1, p is 2, and R₂ and R₂ ' are hydrogen atom.)

According to the method of J. Cole et al., J. Chem. Soc., 244 (1962), a mixture of toluylacetylene (200 mmol), 2-(4-bromophenyl)-1,3-dioxalane (200 mmol), dimethylformamide (500 ml), and copper iodide (I) (300 mmol) was heated while stirring for 5 hours. After allowed to cool, 500 ml of 6M hydrochloric acid was added and stirred for 1 hour. It was extracted with 500 ml of toluene, and the organic layer was washed with water thrice and dried with anhydrous magnesium sulfate. The solvent was distilled off and the residue was purified by a silica gel column chromatography (eluent:toluene) to obtain 120 mmol of 4-(2-(4-methylphenyl)ethynyl)benzaldehyde.

Solution of phenyllithium (corresponding to 125 mmol) in hexane was added dropwise at -78° C. to the mixture of the phosphonium salt of 1-bromo-5-pentene (125 mmol) prepared in Example 1 and 300 ml of THF, and stirred at the same temperature for 1 hour. To this mixture was added dropwise the solution of the 4-(2-(4-methylphenyl)ethynyl)benzaldehyde (120 mmol) obtained by previous procedures in 500 ml of THF while keeping it at -78° C. To the reaction solution was carefully added 50 ml of water and it was gradually brought back to room temperature. Further, 100 ml of water was added, extracted with 100 ml of toluene, and the organic layer was washed with 2N hydrochloric acid and saturated aqueous solution of sodium bicarbonate, and washed with water until it became neutral. After it was dried with anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column chromatography (eluent:heptane) to obtain the subject compound (19 mmol). NMR spectrum, mass spectrum, IR spectrum, and the values of elementary analysis of this compound well supported its structure.

According to the method of Example 3, the following compounds were prepared:

    __________________________________________________________________________     R1         A X1                                                                               B      X2 C      X3 D      W                                    __________________________________________________________________________       205 CH3                                                                                                                  CSTR857##                                                                    .tbd.C                                                                           #STR858##                                                                      #STR859##                             - 206 C3H7                                                                                                              C.tbd.C #                                                                      #STR861##                                                                      #STR862##                             - 207 C4H9                                                                                                              C.tbd.C #                                                                      #STR864##                                                                      #STR865##                             - 208 C5H11                                                                                                             C.tbd.C #                                                                      #STR867##                                                                      #STR868##                             - 209 C5H11                                                                                                             C.tbd.C #                                                                      #STR870##                                                                      #STR871##                             - 210 C5H11                                                                                                             C.tbd.C #                                                                      #STR873##                                                                      #STR874##                             - 211 C5H11                                                                                                             C.tbd.C #                                                                      #STR876##                                                                      #STR877##                             - 212 C3H7                                                                                                              C.tbd.C #                                                                       STR879##                                                                      #STR880##                                                                      #STR881##                             - 213 C3H7                                                                                                              C.tbd.C #                                                                       STR883##                                                                      #STR884##                                                                      #STR885##                             - 214 C3H7                                                                                                              C.tbd.C #                                                                       STR887##                                                                      #STR888##                                                                      #STR889##                             - 215 C4H9                                                                                                              C.tbd.C #                                                                       STR891##                                                                      #STR892##                                                                      #STR893##                             - 216 C5H11                                                                                                             C.tbd.C #                                                                       STR895##                                                                      #STR896##                                                                      #STR897##                             - 217 C5H11                                                                                                             C.tbd.C #                                                                       STR899##                                                                      #STR900##                                                                      #STR901##                             - 218 C3H7                                                                                                               STR902##                                                                      C.tbd.C #                                                                      #STR904##                                                                      #STR905##                             - 219 C3H7                                                                                                               STR906##                                                                      C.tbd.C #                                                                      #STR908##                                                                      #STR909##                             - 220 C4H9                                                                                                               STR910##                                                                      C.tbd.C #                                                                      #STR912##                                                                      #STR913##                             - 221 C5H11                                                                                                              STR914##                                                                      C.tbd.C #                                                                      #STR916##                                                                      #STR917##                             - 222 C5H11                                                                                                              STR918##                                                                      C.tbd.C #                                                                      #STR920##                                                                      #STR921##                             - 223 C5H11                                                                                                              STR922##                                                                      C.tbd.C #                                                                      #STR924##                                                                      #STR925##                             - 224 C5H11                                                                                                              STR926##                                                                      C.tbd.C #                                                                      #STR928##                                                                      #STR929##                             - 225 CH3OCH2CH2                                                                                                         STR930##                                                                      C.tbd.C #                                                                      #STR932##                                                                      #STR933##                             - 226 CH3OCH2CH2CH2                                                                                                      STR934##                                                                      C.tbd.C #                                                                      #STR936##                                                                      #STR937##                             - 227 FCH2CH2                                                                                                            STR938##                                                                      C.tbd.C #                                                                      #STR940##                                                                      #STR941##                             - 228 FCH2CH2CH2                                                                                                         STR942##                                                                      C.tbd.C #                                                                      #STR944##                                                                     ##STR945##                          __________________________________________________________________________

EXAMPLE 4

Preparation of 4-(1,5-hexadienyl)phenyl-4-propylbenzoate ##STR946## (Compound No. 229 expressed by general formula (1) wherein R₁ represents propyl group, X₃ represents --CO₂ --, C and D represent trans-1,4-cyclohexane ring, l, m, and n are 0, o is 1, p is 2, and R₂ and R₂ ' are hydrogen atom.)

Potassium-t-butoxide (100 mmol) was added to the mixture of the phosphonium salt of 1-bromo-5-pentene (100 mmol) prepared in Example 1 and 200 ml of THF, and stirred at room temperature for 1 hour. To this mixture was added dropwise a solution of a commercially available 4-hydroxybenzaldehyde (90 mmol) in 100 ml of THF while keeping it at 0C. After it was stirred at the same temperature for 2 hours, the reaction solution was put in 100 ml of water, and extracted with 200 ml of ether, and the organic layer was washed with water until it became neutral. After it was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column chromatography (eluent:ethyl acetate) to obtain 70 mmol of 4-(cis-1,5-hexedienyl)phenol.

m-Chloroperbenzoic acid (210 mmol) and potassium carbonate (420 mmol) were added to the solution of the compound mentioned above (70 mmol) in 210 ml of methylene chloride and stirred at room temperature for 8 hours. After 200 ml of saturated aqueous solution of sodium thiosulfate was added to the reaction solution and stirred, the organic layer was washed with water thrice and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure to obtain 4-(cis-1,5-hexedienyl)phenoldioxide (50 mmol).

Mixture of the epoxide (50 mmol) mentioned above, dibromotriphenylphosphine dibromide (150 mmol), and 80 ml of toluene was heated while stirring for 3 hours. After cooled down, the reaction solution was put in 300 ml of water, and extracted with 60 ml of ether, and the organic layer was washed with 2M hydrochloric acid and saturated aqueous solution of sodium bicarbonate and washed with water until it became neutral. After it was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column chromatography (eluent:ethyl acetate) to obtain 4-(1,2,5,6-tetrabromohexyl)phenol (25 mmol).

Mixture of the bromide (25 mmol) mentioned above, 200 mmol of metal zinc, and 5 ml of acetic acid was stirred at room temperature for 12 hours. Water in an amount of 25 ml was added and extracted with 25.ml of ether, and the organic layer was washed with water until it became neutral. After it was dried with anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by a silica gel column chromatography (eluent: ethyl acetate) to obtain oily 4-(1,5-hexadienyl)phenol (20 mmol).

Mixture of the 4-(1,5-hexadienyl)phenol (20 mmol) mentioned above, 4-propylbenzoic acid (20 mmol), dicyclohexylcarbodiimide (20 mmol), dimethylaminopyridine (1 mmol), and 10 ml of methylene chloride was stirred at room temperature for 20 hours. The urea derivative thus precipitated was filtered off, the solvent was distilled off under a reduced pressure, and the residue was purified by a silica gel column chromatography (eluent:toluene) to obtain the subject compound in white solid state (13 mmol). NMR spectrum, mass spectrum, IR spectrum, and the values of elementary analysis of this compound well supported its structure.

According to the method of Example 4, the following compounds were prepared:

    __________________________________________________________________________     R1       A      X1 B      X2 C      X3 D      W                                __________________________________________________________________________       229 C3H7                                                                                                                     COO 947##                                                                      #STR948##                                                                      #STR949##                      230 C3H7                                                                        ##STR950 COO                                                                            ##STR9 1##                                                                            ## TR952##                                                       - 231 C5H11                                                                                     ##STR9 COO                                                                            ## TR954##                                                                        ##STR9 5##                                          - 232 C3H7                                                                                                       ## OCO 6##                                                                        ##STR9 7##                                                                             #STR958##                         - 233 C5H11                                                                                                                 OCO 959##                                                                      #STR960##                                                                      #STR961##                         - 234 C3H7                                                                                                                  OCO 962##                                                                       STR963##                                                                      #STR964##                                                                      #STR965##                         - 235 C4H9                                                                                                                  OCO 966##                                                                       STR967##                                                                      #STR968##                                                                      #STR969##                         - 236 C5H11                                                                                                                 OCO 970##                                                                       STR971##                                                                      #STR972##                                                                      #STR973##                         - 237 C5H11                                                                                                                 OCO 974##                                                                       STR975##                                                                      #STR976##                                                                      #STR977##                         - 238 CH3                                                                                                                   COO 978##                                                                       STR979##                                                                      #STR980##                                                                      #STR981##                         - 239 C3H7                                                                                                                  COO 982##                                                                       STR983##                                                                      #STR984##                                                                      #STR985##                         - 240 C2H5                                                                                                                  OCO 986##                                                                       STR987##                                                                      #STR988##                                                                      #STR989##                         - 241 C3H7                                                                                                                  OCO 990##                                                                       STR991##                                                                      #STR992##                                                                      #STR993##                         - 242 C3H7                                                                                                                   STR994##                                                                      OCO 995##                                                                      #STR996##                                                                      #STR997##                         - 243 C5H11                                                                                                                  STR998##                                                                      OCO 999##                                                                      #STR1000##                                                                     #STR1001##                        - 244 C3H7                                                                                                                   STR1002##                                                                     COO 1003##                                                                     #STR1004##                                                                     #STR1005##                        - 245 C5H11                                                                                                                  STR1006##                                                                     COO 1007##                                                                     #STR1008##                                                                     #STR1009##                        - 246 CH3OCH2                                                                                                                STR1010##                                                                     COO 1011##                                                                     #STR1012##                                                                     #STR1013##                        - 247 C5H11                                                                                                                  STR1014##                                                                     C0O 1015##                                                                     #STR1016##                                                                     #STR1017##                        - 248 C3H7                                                                                                                   STR1018##                                                                     OCO 1019##                                                                     #STR1020##                                                                     #STR1021##                        - 249 CH3OCH2CH2                                                                                                             STR1022##                                                                     OCO 1023##                                                                     #STR1024##                                                                     #STR1025##                        - 250 FCH2CH2                                                                                                                STR1026##                                                                     OCO 1027##                                                                     #STR1028##                                                                     #STR1029##                        - 251 C3H7                                                                                                                   STR1030##                                                                     OCO 1031##                                                                      STR1032##                                                                     #STR1033##                                                                     #STR1034##                        - 252 C5H11                                                                                                                  STR1035##                                                                     OCO 1036##                                                                      STR1037##                                                                     #STR1038##                                                                     #STR1039##                        - 253 C3H7                                                                                                                  COO 1040##                                                                      STR1041##                                                                      STR1042##                                                                     #STR1043##                                                                     #STR1044##                        - 254 C3H7                                                                                                                   STR1045##                                                                     OCO 1046##                                                                      STR1047##                                                                     #STR1048##                                                                     #STR1049##                        - 255 C5H11                                                                                                                  STR1050##                                                                     OCO 1051##                                                                      STR1052##                                                                     #STR1053##                                                                     #STR1054##                        - 256 C3H7                                                                                                                   STR1055##                                                                      STR1056##                                                                     OCO 1057##                                                                     #STR1058##                                                                     #STR1059##                        - 257 C5H11                                                                                                                  STR1060##                                                                      STR1061##                                                                     OCO 1062##                                                                     #STR1063##                                                                    ##STR1064##                     __________________________________________________________________________

EXAMPLE 5

Preparation of 4-(4-(4-propylcyclohexyl)phenyldifluoro-methoxy)-1-(1,5-hexadienyl)benzene ##STR1065## (Compound No. 270 expressed by general formula (1) wherein R₁ represents propyl group, X₂ represents a covalent bond, X₃ represents --CF₂ O--, B represents trans-1,4-cyclohexane ring, C and D represent 1,4-phenylene ring, l and n are 0, m and o are 1, p is 2, and R₂ and R₂ ' are hydrogen atom.)

Solution of 4-(4-propylcyclohexyl)bromobenzene (200 ml) in 100 ml of THF was gradually added dropwise to a mixture of metal magnesium (210 mmol) and 10 ml of THF and then further heated under reflux for 1 hour to obtain a grey Grignard reagent. To this reagent was added carbon disulfide (600 mmol) at a temperature lower than 0° C. and then stirred for further 2 hours. Water in an amount of 500 ml was added and extracted with 100 ml of ether thrice. The organic layer was washed with a brine solution twice and dried with magnesium sulfate. The solvent was distilled off under a reduced pressure and the residue was recrystallized from toluene to obtain 98 mmol of 4-(4-propyl-cyclohexyl)thiobenzoic acid.

After the mixture of the thiobenzoic acid (98 mmol) mentioned above and thionyl chloride (500 mmol) was stirred at 50° C. for 5 hours, an excess amount of thionyl chloride was distilled off under a reduced pressure to obtain 97 mmol of corresponding acid chloride.

Acid chloride (97 mmol) obtained by the preceding procedures was added at a temperature lower than 0° C. to the solution of the 4-(1,5-hexadienyl)phenol (80 mmol) prepared in Example 4 in 200 ml of pyridine, and stirred at room temperature for 10 hours. Water in an amount of 500 ml and 200 ml of toluene were added to the solution and stirred. After the organic layer was washed with 200 ml of 2M hydrochloric acid and 200 ml of saturated aqueous solution of sodium bicarbonate, and then washed with water until it became neutral, it was dried with anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and the residue was recrystallized from ethanol 5 times as much as the residue to obtain 4-(1,5-hexadienyl) phenyl-4-(4-propylcyclohexyl)thiobenzoate (61 mmol).

After diethylaminosulfurtrifluoride (122 mmol) was gradually added at -20° C. to the solution of the 4-(1,5-hexadienyl)phenyl-4-(4-propylcyclohexyl)thiobenzoate (61 mmol) in 50 ml of methylene chloride, they were gradually brought back to room temperature and stirred at the same temperature for 3 hours. After 50 ml of water was added to the solution and stirred, the organic layer was washed with water thrice and dried with anhydrous magnesium sulfate. The solvent was distilled off and the residue was purified by a silica gel column chromatography (eluent:heptane) and then recrystallized from ethanol 5 times as much as the residue to obtain the subject compound in white solid state (32 mmol). NMR spectrum, mass spectrum, IR spectrum, and the values of elementary analysis of this compound well supported its structure.

According to the method of Example 5, the following compounds were prepared:

    __________________________________________________________________________     R1    A      X1  B      X2  C      X3  D      W                                __________________________________________________________________________       258 C3H7                                                                                                                     CF2O 066##                                                                     #STR1067##                                                                     #STR1068##                     259 C3H7                                                                        ##STR CF2O                                                                           ##STR1 70##                                                                           ##S R1071##                                                         - 260 C5H11                                                                                   ##STR1 CF2O                                                                           ##S R1073##                                                                        ##STR1 74##                                          - 261 C3H7                                                                                                      ##S OCF2 ##                                                                        ##STR1 76##                                                                            #STR1077##                        - 262 C5H11                                                                                                                 OCF2 078##                                                                     #STR1079##                                                                     #STR1080##                        - 263 C3H7                                                                                                                  OCF2 081##                                                                      STR1082##                                                                     #STR1083##                                                                     #STR1084##                        - 264 C4H9                                                                                                                  OCF2 085##                                                                      STR1086##                                                                     #STR1087##                                                                     #STR1088##                        - 265 C5H11                                                                                                                 OCF2 089##                                                                      STR1090##                                                                     #STR1091##                                                                     #STR1092##                        - 266 C5H11                                                                                                                 OCF2 093##                                                                      STR1094##                                                                     #STR1095##                                                                     #STR1096##                        - 267 CH3                                                                                                                   CF2O 097##                                                                      STR1098##                                                                     #STR1099##                                                                     #STR1100##                        - 268 C3H7                                                                                                                  CF2O 101##                                                                      STR1102##                                                                     #STR1103##                                                                     #STR1104##                        - 269 C2H5                                                                                                                   STR1105##                                                                     CF2O 106##                                                                     #STR1107##                                                                     #STR1108##                        - 270 C3H7                                                                                                                   STR1109##                                                                     CF2O 110##                                                                     #STR1111##                                                                     #STR1112##                        - 271 C3H7                                                                                                                   STR1113##                                                                     OCF2 114##                                                                     #STR1115##                                                                     #STR1116##                        - 272 C5H11                                                                                                                  STR1117##                                                                     OCF2 118##                                                                     #STR1119##                                                                     #STR1120##                        - 273 C3H7                                                                                                                  CF2O 121##                                                                      STR1122##                                                                      STR1123##                                                                     #STR1124##                                                                     #STR1125##                        - 274 C5H11                                                                                                                 OCF2 126##                                                                      STR1127##                                                                      STR1128##                                                                     #STR1129##                                                                     #STR1130##                        - 275 C3H7                                                                                                                   STR1131##                                                                      STR1132##                                                                     CF2O 133##                                                                     #STR1134##                                                                     #STR1135##                        - 276 C5H11                                                                                                                  STR1136##                                                                      STR1137##                                                                     OCF2 138##                                                                     #STR1139##                                                                    ##STR1140##                     __________________________________________________________________________

EXAMPLE 6

Preparation of 4-(4-pentylbenzyloxy)-1-(1,5-hexadienyl) benzene ##STR1141## (Compound No. 279 expressed by general formula (1) wherein R₁ represents pentyl group, X₃ represents --CH₂ O--, C and D represent 1,4-phenylene ring, l, m, and n are 0, o is 1, p is 2, and R₂ and R₂ ' are hydrogen atom.)

Solution of the 4-(1,5-hexadienyl)phenol (500 mmol) obtained by the same method as in Example 4 in 120 ml of THF was added dropwise to a mixture of sodium hydride (120 mmol), 20 ml of THF, and 50 ml of DMF, and stirred for about 2 hours until generation of hydrogen gas ceased. To this solution was added dropwise a solution of 4-pentylbenzylbromide (45 mmol) in 50 ml of THF at a temperature lower than 0° C. and stirred for further 5 hours. Water in an amount of 100 ml and 100 ml of toluene were added to this solution, and the organic layer was washed with 100 ml of 2M hydrochloric acid and 100 ml of saturated aqueous solution of sodium bicarbonate, washed with water until it became neutral, and then dried with anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and the residue was recrystallized from ethanol 5 times as much as the residue to obtain 21 mmol of white oily subject compound. NMR spectrum, mass spectrum, IR spectrum, and the values of elementary analysis of this compound well supported its structure.

According to the method of Example 6, the following compounds were prepared:

    __________________________________________________________________________     R1       A      X1  B      X2  C      X3  D      W                             __________________________________________________________________________       277 C3H7                                                                                                                        CH2O 142##                                                                     #STR1143##                                                                     #STR1144##                  278 C3H7                                                                        ##STR114 CH2O                                                                           ##STR1 46##                                                                           ##S R1147##                                                      - 279 C5H11                                                                                      ##STR1 CH2O                                                                           ##S R1149##                                                                        ##STR1 50##                                       - 280 C3H7                                                                                                         ##S OCH2 ##                                                                        ##STR1 52##                                                                            #STR1153##                     - 281 C5H11                                                                                                                    OCH2 154##                                                                     #STR1155##                                                                     #STR1156##                     - 282 C3H7                                                                                                                     OCH2 157##                                                                      STR1158##                                                                     #STR1159##                                                                     #STR1160##                     - 283 C4H9                                                                                                                     OCH2 161##                                                                      STR1162##                                                                     #STR1163##                                                                     #STR1164##                     - 284 C5H11                                                                                                                    OCH2 165##                                                                      STR1166##                                                                     #STR1167##                                                                     #STR1168##                     - 285 C5H11                                                                                                                    OCH2 169##                                                                      STR1170##                                                                     #STR1171##                                                                     #STR1172##                     - 286 CH3                                                                                                                      CH2O 173##                                                                      STR1174##                                                                     #STR1175##                                                                     #STR1176##                     - 287 C3H7                                                                                                                     CH2O 177##                                                                      STR1178##                                                                     #STR1179##                                                                     #STR1180##                     - 288 C2H5                                                                                                                     OCH2 181##                                                                      STR1182##                                                                     #STR1183##                                                                     #STR1184##                     - 289 C3H7                                                                                                                     OCH2 185##                                                                      STR1186##                                                                     #STR1187##                                                                     #STR1188##                     - 290 C3H7                                                                                                                      STR1189##                                                                     OCH2 190##                                                                     #STR1191##                                                                     #STR1192##                     - 291 C5H11                                                                                                                     STR1193##                                                                     OCH2 194##                                                                     #STR1195##                                                                     #STR1196##                     - 292 C3H7                                                                                                                      STR1197##                                                                     CH2O 198##                                                                     #STR1199##                                                                     #STR1200##                     - 293 C5H11                                                                                                                     STR1201##                                                                     CH2O 202##                                                                     #STR1203##                                                                     #STR1204##                     - 294 CH3OCH2                                                                                                                   STR1205##                                                                     CH2O 206##                                                                     #STR1207##                                                                     #STR1208##                     - 295 C5H11                                                                                                                     STR1209##                                                                     CH2O 210##                                                                     #STR1211##                                                                     #STR1212##                     - 296 C3H7                                                                                                                      STR1213##                                                                     OCH2 214##                                                                     #STR1215##                                                                     #STR1216##                     - 297 CH3OCH2CH2                                                                                                                STR1217##                                                                     OCH2 218##                                                                     #STR1219##                                                                     #STR1220##                     - 298 FCH2CH2                                                                                                                   STR1221##                                                                     OCH2 222##                                                                     #STR1223##                                                                     #STR1224##                     - 299 C3H7                                                                                                                      STR1225##                                                                     OCH2 226##                                                                      STR1227##                                                                     #STR1228##                                                                     #STR1229##                     - 300 C5H11                                                                                                                     STR1230##                                                                     OCH2 231##                                                                      STR1232##                                                                     #STR1233##                                                                     #STR1234##                     - 301 C3H7                                                                                                                     CH2O 235##                                                                      STR1236##                                                                      STR1237##                                                                     #STR1238##                                                                     #STR1239##                     - 302 C3H7                                                                                                                      STR1240##                                                                     OCH2 241##                                                                      STR1242##                                                                     #STR1243##                                                                     #STR1244##                     - 303 C5H11                                                                                                                     STR1245##                                                                     OCH2 246##                                                                      STR1247##                                                                     #STR1248##                                                                     #STR1249##                     - 304 C3H7                                                                                                                      STR1250##                                                                      STR1251##                                                                     OCH2 252##                                                                     #STR1253##                                                                     #STR1254##                     - 305 C5H11                                                                                                                     STR1255##                                                                      STR1256##                                                                     OCH2 257##                                                                     #STR1258##                                                                    ##STR1259##                  __________________________________________________________________________

EXAMPLE 7 (Use Example 1)

Liquid Crystal Composition B1 comprising the following compounds was prepared:

    ______________________________________                                         4-(4-propylcyclohexyl)benzonitrile                                                                        24%                                                   4-(4-pentylcyclohexyl)benzonitrile 36%                                         4-(4-heptylcyclohexyl)benzonitrile 25%                                         4-(4-(4-pentylcyclohexyl)phenyl)benzonitrile 15%                             ______________________________________                                    

This nematic liquid crystal composition had a clearing point of 72.4° C., threshold voltage of 1.78 V at a cell thickness of 9 μm, value of dielectric anisotropy of 11.0, optical anisotropy of 0.137, and viscosity of 27.0 mPa.s at 20° C. This liquid crystal composition in an amount of 85% was mixed with 15% of the compound (Compound No. 8) of the present invention obtained in Example 1 to prepare Liquid Crystal Composition A1. This composition had a clearing point of 75.0° C., threshold voltage of 1.84 V at a cell thickness of 8.9 μm, value of dielectric anisotropy of 9.6, optical anisotropy of 0.126, viscosity of 20.7 mPa.s at 20° C., and ratio of elastic constants K₃₃ /K₁₁ of 2.02. Further, the extrapolation value calculated from the mixing ratio were 89.7° C. for the clearing point, 1.7 for the value of dielectric anisotropy, 0.063 for the optical anisotropy, and -15.0 mPa.s for the viscosity, respectively.

While this liquid crystal composition was left in a freezer at -20° C. for 60 days, precipitation of crystals was not noticed.

EXAMPLE 8 (Use Example 2)

Clearing point, viscosity at 20° C., optical anisotropy at 25° C., and threshold voltage at a cell thickness of 8.7 μm of the liquid crystal composition shown in Composition Example 1 were determined to find to be 101.9° C., 16.02 mPa.s, 0.132, and 2.10 V, respectively.

Comparative Example 1

The following compound ##STR1260## prepared by the method described in Laid-open Japanese Patent Publication No. Hei 6-151447 was added in an amount of 15% to the Liquid Crystal Composition B1 to prepare Liquid Crystal Composition A2. Al obtained in Example 7 and A2 were simultaneously heated at 100° C. for 2 hours and change of clearing point was observed.

    ______________________________________                                                      Clearing point                                                                            Clearing point                                           Composition before heating after heating                                     ______________________________________                                         A1           75.0° C.                                                                           74.8° C.                                          A2 62.8° C. 55.1° C.                                           ______________________________________                                    

It was found that whereas the clearing point of Liquid Crystal Composition A2 was reduced by about 7° C., the reduction of clearing point of Liquid Crystal Composition A1 was only 0.2° C., and thus that the compound of general formula (1) are extremely stable.

According to the procedures mentioned above, the following compositions were prepared and their physical parameters were determined:

In the following composition examples, compounds are designated by code addresses according to the understanding in the following Table. That is, left side terminal group is expressed by a--, aO--, aOb--, Va--, aVb--, or aVbVd--; bonding group is expressed by 2, E, T, V, or CF20; ring structure is expressed by B. B(F), B(F,F), H, Py, D, or Ch; and right side terminal group is expressed by --F, --CL, --C, --CF3, --OCF3, --OCF2H, --w, --Ow, or EMe.

    __________________________________________________________________________     Left side terminal                                                               group Symbol Bonding group Symbol                                            __________________________________________________________________________       C.sub.a H.sub.2a+1 -- a-- --CH.sub.2 CH.sub.2 -- 2                             C.sub.a H.sub.2a+1 O-- aO-- --COO-- E                                          C.sub.a H.sub.2a+1 OC.sub.b H.sub.2b -- aOb-- --C.tbd.C-- T                    CH.sub.2 ═CHC.sub.a H.sub.2a -- Va-- --CH═CH-- V                       C.sub.a H.sub.2a+1 CH═CHC.sub.b H.sub.2b -- aVb-- --CF.sub.2 O--                                          CF2O                                            C.sub.a H.sub.2a+1 CH═CHC.sub.b H.sub.2b CH═CHC.sub.d H.sub.2d                                        -- aVbVd--                                    __________________________________________________________________________                         Right side terminal                                          Ring structure Symbol group Symbol                                           __________________________________________________________________________                                      B TR1261##                                                                   --F --F                                            -                                                                                                            B(F) --Cl --CL                                   -                                                                                                            B(F,F) --CN --C                                  -                                                                                                            H --CF.sub.3 --CF3                               -                                                                                                            Py --OCF.sub.3 --OCF3                            -                                                                                                            D --OCF.sub.2 H --OCF2H                          -                                                                                                            CH --C.sub.w H.sub.2w+1 --w                      -   --OC.sub.w H.sub.2w+1 --Ow                                                  --COOCH3 --EMe                                                             __________________________________________________________________________

EXAMPLE 9 (Use Example 3)

    ______________________________________                                         V2V--HBB-2 (Compound No. 62)                                                                        10%                                                         1V2--BEB(F,F)--C 8%                                                            3-HB--C 24%                                                                    3-HB--O2 5%                                                                    3-HH-4 11%                                                                     3-HH-5 5%                                                                      3-HHB-1 10%                                                                    3-HHB-3 11%                                                                    3-H2BTB-2 4%                                                                   3-H2BTB-3 4%                                                                   3-H2BEB-4 4%                                                                   3-HB(F)TB-2 2%                                                                 3-HB(F)TB-3 2%                                                               ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     100.6                                                          Viscosity [mPa · s] 17.8                                              Optical anisotropy 0.132                                                       Threshold voltage [V] 2.09                                                   ______________________________________                                    

EXAMPLE 10 (Use Example 4)

    ______________________________________                                         V2V--HH-1 (Compound No. 1)                                                                          18%                                                         1V2--BEB(F,F)--C 9%                                                            3-HB--C 21%                                                                    3-HHB-1 10%                                                                    3-HHB-3 15%                                                                    2-HHB-1 2%                                                                     3-HHB--O1 3%                                                                   3-H2BTB-2 4%                                                                   3-H2BTB-3 4%                                                                   3-H3BTB-4 4%                                                                   3-HB(F)TB-2 4%                                                                 3-HB(F)TB-3 3%                                                                 3-HB(F)TB-4 3%                                                               ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     99.8                                                           Viscosity [mPa · s] 16.2                                              Optical anisotropy 0.135                                                       Threshold voltage [V] 2.01                                                   ______________________________________                                    

EXAMPLE 11 (Use Example 5)

    ______________________________________                                         V2V--HB--C (Compound No. 16)                                                                         14%                                                        1V2--BEB(F,F)--C 8%                                                            3-HB--C 10%                                                                    3-HB--CO2 7%                                                                   3-HH-4 11%                                                                     3-HH-5 5%                                                                      3-HHB-1 10%                                                                    3-HHB-3 15%                                                                    3-H2BTB-2 4%                                                                   3-H2BTB-3 4%                                                                   3-H2BTB-4 4%                                                                   3-HB(F)TB-2 2%                                                                 3-HB(F)TB-3 3%                                                                 3-HB(F)TB-4 3%                                                               ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     100.2                                                          Viscosity [mPa · s] 17.2                                              Optical anisotropy 0.132                                                       Threshold voltage [V] 2.06                                                   ______________________________________                                    

EXAMPLE 12 (Use Example 6)

    ______________________________________                                         V2V--HH-4 (Compound No. 7)                                                                          15%                                                         1V2--BEB(F,F)--C 8%                                                            3-HB--C 24%                                                                    3-HB--O2 6%                                                                    3-HHB-1 10%                                                                    3-HHB-3 15%                                                                    2-HHB-1 2%                                                                     3-H2BTB-2 4%                                                                   3-H2BTB-3 4%                                                                   3-H2BTB-4 4%                                                                   3-HB(F)TB-3 4%                                                                 3-HB(F)TB-4 4%                                                               ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     100.6                                                          Viscosity [mPa · s] 18.1                                              Optical anisotropy 0.133                                                       Threshold voltage [V] 2.05                                                   ______________________________________                                    

EXAMPLE 13 (Use Example 7)

    ______________________________________                                         V2V--HH-3 (Compound No. 3)                                                                           5%                                                         V2V2--HH-5 (Compound No. 172) 10%                                              3-PyB(F)--F 8%                                                                 2-HB(F)--C 8%                                                                  3-HB(F)--C 8%                                                                  3-HB--C 4%                                                                     2-HHB(F)--F 6%                                                                 3-HHB(F)--F 6%                                                                 5-HHB(F)--F 6%                                                                 3-HHB-1 9%                                                                     3-HHB-3 8%                                                                     3-HHB--O1 3%                                                                   2-HHB(F)--C 3%                                                                 3-HHB(F)--C 7%                                                                 3-PyBB--F 3%                                                                   4-PyBB--F 3%                                                                   5-PyB--F 3%                                                                  ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     87.5                                                           Viscosity [mPa · s] 22.4                                              Optical anisotropy 0.109                                                       Dielectric anisotropy 9.4                                                      Threshold voltage [V] 1.60                                                   ______________________________________                                    

EXAMPLE 14 (Use Example 8)

    ______________________________________                                         V2V--HBB-2 (Compound 62)                                                                            5%                                                          V2V--HB--C (Compound 16) 8%                                                    V2--HB--C 10%                                                                  1V2--HB--C 10%                                                                 3-HB--C 20%                                                                    5-HB--C 10%                                                                    2-PyB-2 3%                                                                     3-PyB-2 3%                                                                     4-PyB-2 3%                                                                     3-HHB-1 5%                                                                     3-HHB-3 5%                                                                     3-HHB--O1 5%                                                                   3-H2BTB-2 3%                                                                   2-PyBH-3 2%                                                                    3-PyBH-3 2%                                                                    3-PyBB--F 2%                                                                   2-DB--C 2%                                                                     3-DB--C 2%                                                                   ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     76.0                                                           Viscosity [mPa · s] 21.0                                              Optical anisotropy 0.139                                                       Dielectric anisotropy 9.5                                                      Threshold voltage [V] 1.70                                                   ______________________________________                                    

EXAMPLE 15 (Use Example 9)

    ______________________________________                                         V2V--HH-1 (Compound No. 1)                                                                           3%                                                         V2V--HH-5 (Compound No. 8) 7%                                                  V2V--HB--C (Compound No. 16) 5%                                                V2--HB--C 8%                                                                   1V2--HB--C 8%                                                                  3-HB--C 8%                                                                     5-HB--C 10%                                                                    1O1--HB--C 8%                                                                  2O1--HB--C 5%                                                                  2-BTB--O1 2%                                                                   3-BTB--O1 2%                                                                   4-BTB--O1 2%                                                                   4-BTB--O2 2%                                                                   5-BTB--O1 2%                                                                   V2--HH-3 8%                                                                    3-HHB-1 5%                                                                     3-HHB-3 5%                                                                     3-HHB--C 10%                                                                 ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     75.5                                                           Viscosity [mPa · s] 18.8                                              Optical anisotropy 0.125                                                       Dielectric anisotropy 8.4                                                      Threshold voltage [V] 1.76                                                   ______________________________________                                    

EXAMPLE 16 (Use Example 10)

    ______________________________________                                         V2V--HB--C (Compound No. 16)                                                                         5.0%                                                       V2V--HH-3 (Compound No. 3) 5.0%                                                V2V--HH-4 (Compound No. 7) 5.0%                                                2-BB--C 6.0%                                                                   4-BB--C 6.0%                                                                   5-BB--C 6.0%                                                                   2-HB--C 10.0%                                                                  3-HB--C 10.0%                                                                  3-PyB-4 1.5%                                                                   4-PyB-4 1.5%                                                                   6-PyB-4 1.5%                                                                   3-PyB-5 1.5%                                                                   4-PyB-5 1.5%                                                                   6-PyB-5 1.5%                                                                   2-HHB-1 3.0%                                                                   3-HHB-1 5.0%                                                                   3-HHB-3 8.0%                                                                   3-HHB--O1 3.0%                                                                 3-HHB--F 3.0%                                                                  2-PyB--O2 2.0%                                                                 3-PyB--O2 2.0%                                                                 2-HHB--C 4.0%                                                                  3-HHB--C 4.0%                                                                  4-HHB--C 4.0%                                                                ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     78.8                                                           Viscosity [mPa · s] 21.9                                              Optical anisotropy 0.135                                                       Dielectric anisotropy 8.3                                                      Threshold voltage [V] 1.73                                                   ______________________________________                                    

EXAMPLE 17 (Use Example 11)

    ______________________________________                                         V2V1--HH-5 (Compound No. 170)                                                                        5%                                                         V2V--H2H-3 (Compound No. 9) 5%                                                 2O1--BEB(F)--C 6%                                                              3O1--BEB(F)--C 6%                                                              1O1--HB--C 5%                                                                  2-HB--C 20%                                                                    3-HB--C 15%                                                                    2-HHB--C 4%                                                                    3-HHB--C 4%                                                                    4-HHB--C 4%                                                                    3-PyBB--F 3%                                                                   1O1--HH-5 8%                                                                   3-HHB-1 3%                                                                     3-HHEB--F 3%                                                                   5-HHEB--F 3%                                                                   3-PyBB-2 3%                                                                    4-PyBB-3 3%                                                                  ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     67.7                                                           Viscosity [mPa · s] 26.9                                              Optical anisotropy 0.119                                                       Dielectric anisotropy 12.2                                                     Threshold voltage [V] 1.24                                                   ______________________________________                                    

EXAMPLE 18 (Use Example 12)

    ______________________________________                                         V2V-HHB(F)-F (Compound No. 178)                                                                      5%                                                         V2V-H2H-3 (Compound No. 9) 10%                                                 V2V-HB-C (Compound No. 16) 3%                                                  3-HB-C 10%                                                                     1O1-HB-C 8%                                                                    2-BTB-1 4%                                                                     1-BTB-6 8%                                                                     4-BTB-4 4%                                                                     3-HHB-C 3%                                                                     2-H2HB(F)-F 10%                                                                3-H2HB(F)-F 5%                                                                 5-H2HB(F)-F 10%                                                                3-HHB-O1 3%                                                                    3-HHB-1 7%                                                                     V-HHB-1 3%                                                                     3-HB(F)TB-2 3%                                                               ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     82.6                                                           Viscosity [mPa · s] 19.4                                              Optical anisotropy 0.121                                                       Dielectric anisotropy 5.6                                                      Threshold voltage [V] 2.11                                                   ______________________________________                                    

EXAMPLE 19 (Use Example 13)

    ______________________________________                                         V2V--H2H-3 (Compound No. 9)                                                                          10%                                                        V2V--HBB-2 (Compound No. 62) 5%                                                V2V2--HH-5 (Compound No. 172) 7%                                               2-HB(F)--C 3%                                                                  4-HB(F)--C 3%                                                                  5-HB(F)--C 3%                                                                  2-BEB--C 3%                                                                    1O--BEB-2 5%                                                                   5-HEB--F 4%                                                                    7-HEB--F 4%                                                                    3-HEB--O4 8%                                                                   4-HEB--O2 6%                                                                   5-HEB--O1 6%                                                                   3-HEB--O2 5%                                                                   5-HEB--O2 4%                                                                   4-HEB--O4 8%                                                                   3-HHB-1 5%                                                                     3-HHB-3 5%                                                                     3-HHB--O1 3%                                                                   3-HEBEB--F 3%                                                                ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     76.8                                                           Viscosity [mPa · s] 20.9                                              Optical anisotropy 0.094                                                       Dielectric anisotropy 2.7                                                      Threshold voltage [V] 2.56                                                   ______________________________________                                    

EXAMPLE 20 (Use Example 14)

    ______________________________________                                         V2V--HH-3 (Compound No. 3)                                                                           5%                                                         V2V--HH-4 (Compound No. 7) 5%                                                  V2V1--HH-5 (Compound No. 170) 5%                                               3-PyB(F)--F 8%                                                                 3-PyBB--F 5%                                                                   4-PyBB--F 5%                                                                   5-PyBB--F 5%                                                                   2-PyB-2 5%                                                                     3-PyB-2 5%                                                                     4-PyB-2 5%                                                                     3-HEB--O4 6%                                                                   4-HEB--O2 6%                                                                   5-HEB--O2 6%                                                                   3-HH--EMe 3%                                                                   2-H2BTB-4 5%                                                                   3-H2BTB-4 5%                                                                   3-HHB-1 6%                                                                     3-HHB-3 6%                                                                     3-HHEBB--C 2%                                                                  3-HBEBB--C 2%                                                                ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     80.3                                                           Viscosity [mPa · s] 22.5                                              Optical anisotropy 0.142                                                       Dielectric anisotropy 3.6                                                      Threshold voltage [V] 2.47                                                   ______________________________________                                    

EXAMPLE 21 (Use Example 15)

    ______________________________________                                         V2V--HH-3 (Compound No. 3)                                                                          5%                                                          V2V--HH-4 (Compound No. 7) 5%                                                  V2V--HH-5 (Compound No. 8) 6%                                                  7-HB(F)--F 4%                                                                  5-H2B(F)--F 6%                                                                 2-HHB(F)--F 12%                                                                3-HHB(F)--F 12%                                                                5-HHB(F)--F 12%                                                                2-H2HB(F)--F 2%                                                                3-H2HB(F)--F 1%                                                                5-H2HB(F)--F 2%                                                                2-HBB(F)--F 4%                                                                 3-HBB(F)--F 4%                                                                 5-HBB(F)--F 8%                                                                 2-HBB--F 3%                                                                    3-HBB--F 3%                                                                    5-HBB--F 2%                                                                    3-HHB--F 3%                                                                    3-HHB-1 6%                                                                   ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     91.9                                                           Viscosity [mPa · s] 19.1                                              Optical anisotropy 0.088                                                       Dielectric anisotropy 3.5                                                      Threshold voltage [V] 2.55                                                   ______________________________________                                    

EXAMPLE 22 (Use Example 16)

    ______________________________________                                         V2V--HHB(F,F)--F (Compound No. 179)                                                                    5%                                                       V2V--HH-5 (Compound No. 8) 5%                                                  V1V--HH-5 (Compound No. 173) 3%                                                7-HB(F,F)--F 8%                                                                3-HHB(F,F)--F 3%                                                               4-HHB(F,F)--F 3%                                                               3-H2HB(F,F)--F 10%                                                             4-H2HB(F,F)--F 8%                                                              5-H2HB(F,F)--F 8%                                                              3-HH2B(F,F)--F 5%                                                              5-HH2B(F,F)--F 5%                                                              3-HBB(F,F)--F 8%                                                               5-HBB(F,F)--F 8%                                                               3-H2BB(F,F)--F 3%                                                              5-H2BB(F,F)--F 3%                                                              2-HHB--OCF3 3%                                                                 5-HHB--OCF3 3%                                                                 3-HH2B--OCF3 5%                                                                5-HH2B--OCF3 4%                                                              ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     74.7                                                           Viscosity [mPa · s] 22.1                                              Optical anisotropy 0.083                                                       Dielectric anisotropy 5.6                                                      Threshold voltage [V] 1.06                                                   ______________________________________                                    

EXAMPLE 23 (Use Example 17)

    ______________________________________                                         V2V--HHB(F,F)--F (Compound No. 179)                                                                    10%                                                      V2V2--HH-4 (Compound No. 172) 6%                                               3-H2HB(F,F)--F 7%                                                              4-H2HB(F,F)--F 7%                                                              5-H2HB(F,F)--F 6%                                                              3-HH2B(F,F)--F 5%                                                              3-HBB(F,F)--F 16%                                                              5-HBB(F,F)--F 16%                                                              3-H2BB(F,F)--F 5%                                                              4-H2BB(F,F)--F 5%                                                              5-H2BB(F,F)--F 5%                                                              3-HBEB(F,F)--F 2%                                                              5-HBEB(F,F)--F 2%                                                              3-HHEB(F,F)--F 3%                                                              3-H2HB--OCF3 3%                                                                5-H2HB--OCF3 2%                                                              ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     74.8                                                           Viscosity [mPa · s] 26.7                                              Optical anisotropy 0.101                                                       Dielectric anisotropy 8.7                                                      Threshold voltage [V] 1.63                                                   ______________________________________                                    

EXAMPLE 24 (Use Example 18)

    ______________________________________                                         V2V--HHB(F,F)--F (Compound No. 179)                                                                    7.0%                                                     V2V--HHB(F)--F (Compound No. 178) 7.0%                                         V2V--H2H-3 (Compound No. 9) 7.0%                                               3-HB--CL 5.0%                                                                  2-HHB--CL 4.0%                                                                 4-HHB--CL 8.0%                                                                 5-HHB--CL 4.0%                                                                 7-HB(F,F)--F 2.0%                                                              2-HBB(F)--F 4.5%                                                               3-HBB(F)--F 4.5%                                                               5-HBB(F)--F 9.0%                                                               3-HBB(F,F)--F 10.0%                                                            5-HBB(F,F)--F 10.0%                                                            3-HB(F)VB-2 4.0%                                                               3-HB(F)VB-3 4.0%                                                               3-H2HB(F)--CL 4.0%                                                             5-HB--F 3.0%                                                                   7-HB--F 3.0%                                                                 ______________________________________                                    

Physical parameters of the liquid crystal composition shown above were as follows:

    ______________________________________                                         Clearing point [° C.]                                                                     94.4                                                           Viscosity [mPa · s] 21.3                                              Optical anisotropy 0.119                                                       Dielectric anisotropy 5.3                                                      Threshold voltage [V] 2.22                                                   ______________________________________                                    

APPLICATION IN INDUSTRY

Liquid crystalline compounds of the present invention have a large ratio of elastic constants, have a low viscosity compared with existing liquid crystalline compounds, are excellent in miscibility with other liquid crystalline compounds, particularly in that miscibility at low temperatures, and are chemically stable. Thus, the liquid crystal compositions having excellent physical properties, that is, steep threshold characteristics and high response speed can be obtained by including the liquid crystalline compounds in a liquid crystal composition. 

What is claimed is:
 1. A liquid crystalline compound expressed by the following general formula (1) ##STR1268## wherein R₁ represents cyano group, a halogen atom, or a straight or branched alkyl group or halogenated alkyl group having 1 to 20 carbon atoms, one or not-adjacent two CH₂ groups in the alkyl or halogenated alkyl group may be replaced by oxygen atom or --CH═CH-- group; R₂ and R₂ ' represent hydrogen atom, a halogen atom, or an alkyl group having 1 to 9 carbon atoms; X₁, X₂ and X₃ independently represent--CH₂ CH₂ --, --CO--O--, --O--CO--, --CH═CH--, --C.tbd.C--, --(CH₂)₄ --, --CF₂ O--, --OCF₂ --, --CH₂ O--, --OCH₂ --, or a covalent bond; rings A, B, C, and D independently represent 1,4-phenylene ring, trans-1,4-cyclohexylene ring, cyclobutane ring, or spiroheptane ring, respectively, hydrogen atom(s) in these rings may be replaced by halogen atom(s) and carbon atom(s) in these rings may be replaced by up to three nitrogen atom(s) or up to two oxygen atom(s) provided that two rings in which carbon atom is replaced by nitrogen atom or oxygen atom are not bonded with a covalent bond, and provided that ring D represents trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl; l and m are independently an integer of 0 or 1, o is 1, n is an integer of 0 to 3; and p is an integer of 3 to
 5. 2. A liquid crystal composition comprising at least two components and containing at least one compound defined in claim 1 in at least one of the components.
 3. A liquid crystal display device comprising a liquid crystal composition defined in claim
 2. 4. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound expressed by following general formula (1) ##STR1269## wherein R₁ represents cyano group, a halogen atom, or a straight or branched alkyl group or halogenated alkyl group having 1 to 20 carbon atoms, one or not-adjacent two CH₂ groups in the alkyl or halogenated alkyl group may be replaced by oxygen atom or --CH═CH-- group; R₂ and R₂ ' represent hydrogen atom, a halogen atom, or an alkyl group having 1 to 9 carbon atoms; X₁, X₂ and X₃ independently represent--CH₂ CH₂ --, --CO--O--, --O--CO--, --CH═CH--, --C.tbd.C--, --(CH₂)₄ --, --CF₂ O--, --OCF₂ --, --CH₂ O--, --OCH₂ --, or a covalent bond; rings A, B, C, and D independently represent 1,4-phenylene ring, trans-1,4-cyclohexylene ring, cyclobutane ring, or spiroheptane ring, respectively, hydrogen atom(s) in these rings may be replaced by halogen atom(s) and carbon atom(s) in these rings may be replaced by up to three nitrogen atom(s) or up to two oxygen atom(s) provided that two rings in which carbon atom is replaced by nitrogen atom or oxygen atom are not bonded with a covalent bond, and provided that ring D represents trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl; l and m are independently an integer of 0 or 1, o is 1, n is an integer of 0 to 3; and p is an integer of 2 to 5, and as a second component, one or more compounds selected from the group consisting of the compounds expressed by the general formula (2), (3), or (4) ##STR1270## in which R₃ represents an alkyl group having 1 to 10 carbon atoms, Y represents F or Cl, Q₁ and Q₂ independently represent H or F, r is 1 or 2, and Z, and Z₂ independently represent --CH₂ CH₂ -- or a covalent bond.
 5. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound expressed by following general formula (1) ##STR1271## wherein R₁ represents cyano group, a halogen atom, or a straight or branched alkyl group or halogenated alkyl group having 1 to 20 carbon atoms, one or not-adjacent two CH₂ groups in the alkyl or halogenated alkyl group may be replaced by oxygen atom or --CH═CH-- group; R₂ and R₂ ' represent hydrogen atom, a halogen atom, or an alkyl group having 1 to 9 carbon atoms; X₁, X₂ and X₃ independently represent--CH₂ CH₂ --, --CO--O--, --O--CO--, --CH═CH--, --C.tbd.C--, --(CH₂)₄ --, --CF₂ O--, --OCF₂ --, --CH₂ O--, --OCH₂ --, or a covalent bond; rings A, B, C, and D independently represent 1,4-phenylene ring, trans-1,4-cyclohexylene ring, cyclobutane ring, or spiroheptane ring, respectively, hydrogen atom(s) in these rings may be replaced by halogen atom(s) and carbon atom(s) in these rings may be replaced by up to three nitrogen atom(s) or up to two oxygen atom(s) provided that two rings in which carbon atom is replaced by nitrogen atom or oxygen atom are not bonded with a covalent bond, and provided that ring D represents trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl; l and m are independently an integer of 0 or 1, o is 1, n is an integer of 0 to 3; and p is an integer of 2 to 5, and as a second component, one or more compounds selected from the group consisting of the compounds expressed by the general formula (5), (6), (7), (8), or (9) ##STR1272## in which R₄ represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in either case any methylene group (--CH₂ --) in the alkyl or alkenyl group may be replaced by oxygen atom (--O--) provided that in no case two or more methylene groups are continuously replaced by oxygen atom; Z₃ represents --CH₂ CH₂ --, --COO--, or a covalent bond; Q₃ and Q₄ represent H or F, E represents cyclohexylene ring, benzene ring, or 1,3-dioxane ring, and s is an integer of 0 or 1, ##STR1273## in which R₅ represents an alkyl group having 1 to 10 carbon atoms, Q₅ represents H or F, and k is an integer of 0 or 1; ##STR1274## in which R6 represents an alkyl group having 1 to 10 carbon atoms, G represents cyclohexane ring or benzene ring, Q₆ and Q₇ independently represent H or F, Z₄ represents --COO-- or a covalent bond, and h is an integer of 0 or 1,

    R.sub.7 --(H)--Z.sub.5 --(J)--R.sub.8                      ( 8)

in which R₇ and R₈ independently represent an alkyl group, alkyloxy group, or alkyloxymethyl group having 1 to 10 carbon atoms, H represents cyclohexane ring, pyrimidine ring, or benzene ring; J represents cyclohexane ring or benzene ring, Z₅ represents --C.tbd.C--, --COO--, --CH₂ CH₂ --, or a covalent bond, ##STR1275## in which R₉ represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, R₁₀ represents an alkyl group, alkyloxy group, or alkoxymethyl group having 1 to 10 carbon atoms, K represents cyclohexane ring or pyrimidine ring, each of L and M independently represent cyclohexane ring or benzene ring, Z₆ represents --COO--, --CH₂ CH₂ --, or a covalent bond, Z₇ represents --C.tbd.C--,--COO--, or a covalent bond, and Q₈ represents H or F.
 6. A liquid crystal display device comprising a liquid crystal composition defined in claim
 4. 7. A liquid crystal display device comprising a liquid crystal composition defined in claim
 5. 